EP3666808A1 - Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same - Google Patents
Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same Download PDFInfo
- Publication number
- EP3666808A1 EP3666808A1 EP20153362.7A EP20153362A EP3666808A1 EP 3666808 A1 EP3666808 A1 EP 3666808A1 EP 20153362 A EP20153362 A EP 20153362A EP 3666808 A1 EP3666808 A1 EP 3666808A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydroxyl
- silylated
- pressure sensitive
- sensitive adhesive
- terminated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 40
- 239000002904 solvent Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims description 58
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 60
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 44
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- 229920002635 polyurethane Polymers 0.000 claims description 28
- 239000004814 polyurethane Substances 0.000 claims description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 22
- 229910000077 silane Inorganic materials 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 15
- 150000003077 polyols Chemical class 0.000 claims description 15
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 10
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000002318 adhesion promoter Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 239000013008 thixotropic agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- 230000001070 adhesive effect Effects 0.000 description 49
- 239000000853 adhesive Substances 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 19
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 19
- 238000006884 silylation reaction Methods 0.000 description 19
- 238000013019 agitation Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 239000012299 nitrogen atmosphere Substances 0.000 description 18
- -1 vinyl compound Chemical class 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- 229920004943 Delrin® Polymers 0.000 description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 229940093499 ethyl acetate Drugs 0.000 description 13
- 235000019439 ethyl acetate Nutrition 0.000 description 13
- 229920002857 polybutadiene Polymers 0.000 description 13
- 239000005062 Polybutadiene Substances 0.000 description 12
- 239000004342 Benzoyl peroxide Substances 0.000 description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 10
- FRDNYWXDODPUJV-UHFFFAOYSA-N n-ethyl-2-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CCNCC(C)C[Si](OC)(OC)OC FRDNYWXDODPUJV-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 229920006267 polyester film Polymers 0.000 description 9
- FGPCETMNRYMFJR-UHFFFAOYSA-L [7,7-dimethyloctanoyloxy(dimethyl)stannyl] 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCC(C)(C)C FGPCETMNRYMFJR-UHFFFAOYSA-L 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 229920006337 unsaturated polyester resin Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003522 acrylic cement Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 3
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GKYGYWOJHVZUTN-UHFFFAOYSA-N (1-methyl-6-triethoxysilylcyclohexa-2,4-dien-1-yl)methanethiol Chemical compound CCO[Si](OCC)(OCC)C1C=CC=CC1(C)CS GKYGYWOJHVZUTN-UHFFFAOYSA-N 0.000 description 2
- RKBANWCUDWRSJO-UHFFFAOYSA-N (1-methyl-6-trimethoxysilylcyclohexa-2,4-dien-1-yl)methanethiol Chemical compound CO[Si](OC)(OC)C1C=CC=CC1(C)CS RKBANWCUDWRSJO-UHFFFAOYSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- MGSDBAGXQUCIFV-UHFFFAOYSA-N 1-[dimethoxy(methyl)silyl]pentane-3-thiol Chemical compound CCC(S)CC[Si](C)(OC)OC MGSDBAGXQUCIFV-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- ZARCFEHBDQIZSJ-UHFFFAOYSA-N 1-triethoxysilylpropane-2-thiol Chemical compound CCO[Si](CC(C)S)(OCC)OCC ZARCFEHBDQIZSJ-UHFFFAOYSA-N 0.000 description 2
- BZBKNKKRTDNXMP-UHFFFAOYSA-N 1-trioctoxysilylpropane-2-thiol Chemical compound CCCCCCCCO[Si](CC(C)S)(OCCCCCCCC)OCCCCCCCC BZBKNKKRTDNXMP-UHFFFAOYSA-N 0.000 description 2
- HUOUUBXYBKHMRJ-UHFFFAOYSA-N 1-tripropoxysilylpropane-2-thiol Chemical compound CCCO[Si](CC(C)S)(OCCC)OCCC HUOUUBXYBKHMRJ-UHFFFAOYSA-N 0.000 description 2
- LAGFJUQEHPLLIW-UHFFFAOYSA-N 12-triethoxysilyldodecane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCCCCCCCCCCS LAGFJUQEHPLLIW-UHFFFAOYSA-N 0.000 description 2
- VREPHMROZZKOOL-UHFFFAOYSA-N 12-trimethoxysilyldodecane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCCCCCCCCCS VREPHMROZZKOOL-UHFFFAOYSA-N 0.000 description 2
- OHKKNEALKRUZOE-UHFFFAOYSA-N 18-[methoxy(dimethyl)silyl]octadecane-1-thiol Chemical compound CO[Si](C)(C)CCCCCCCCCCCCCCCCCCS OHKKNEALKRUZOE-UHFFFAOYSA-N 0.000 description 2
- UAXHQOHEACNJSR-UHFFFAOYSA-N 18-trimethoxysilyloctadecane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCCCCCCCCCCCCCCCS UAXHQOHEACNJSR-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- ZAEPYIXIHJSMDG-UHFFFAOYSA-N 2-[ethoxy(dimethoxy)silyl]ethanethiol Chemical compound CCO[Si](OC)(OC)CCS ZAEPYIXIHJSMDG-UHFFFAOYSA-N 0.000 description 2
- PABWYMSXHPGZFP-UHFFFAOYSA-N 2-methyl-3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC(C)C[Si](OC)(OC)OC PABWYMSXHPGZFP-UHFFFAOYSA-N 0.000 description 2
- NYLOHBUGPHJQSL-UHFFFAOYSA-N 2-methyl-3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CC(C)CS NYLOHBUGPHJQSL-UHFFFAOYSA-N 0.000 description 2
- BMPPHVYQZALIQK-UHFFFAOYSA-N 2-methyl-6-triethoxysilylbenzenethiol Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC(C)=C1S BMPPHVYQZALIQK-UHFFFAOYSA-N 0.000 description 2
- JEELSXJQQHJRII-UHFFFAOYSA-N 2-methyl-6-trimethoxysilylbenzenethiol Chemical compound CO[Si](OC)(OC)C1=CC=CC(C)=C1S JEELSXJQQHJRII-UHFFFAOYSA-N 0.000 description 2
- VGRXLVBQMDBFPP-UHFFFAOYSA-N 2-methyl-n-(2-methyl-3-trimethoxysilylpropyl)-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CC(C)CNCC(C)C[Si](OC)(OC)OC VGRXLVBQMDBFPP-UHFFFAOYSA-N 0.000 description 2
- GORJNOVMWXWIJZ-UHFFFAOYSA-N 2-tri(butan-2-yloxy)silylethanethiol Chemical compound CCC(C)O[Si](CCS)(OC(C)CC)OC(C)CC GORJNOVMWXWIJZ-UHFFFAOYSA-N 0.000 description 2
- WJSLVIWRMKEJEJ-UHFFFAOYSA-N 2-triethoxysilylbenzenethiol Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1S WJSLVIWRMKEJEJ-UHFFFAOYSA-N 0.000 description 2
- UANAJLMWAZQBKE-UHFFFAOYSA-N 2-trimethoxysilylbenzenethiol Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1S UANAJLMWAZQBKE-UHFFFAOYSA-N 0.000 description 2
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 2
- UZEBPNPRXOYGRA-UHFFFAOYSA-N 2-tripropoxysilylethanethiol Chemical compound CCCO[Si](CCS)(OCCC)OCCC UZEBPNPRXOYGRA-UHFFFAOYSA-N 0.000 description 2
- IFAPXTBWPQMLAF-UHFFFAOYSA-N 3-(diethoxymethylsilyl)-N-ethyl-2-methylpropan-1-amine Chemical compound CCNCC(C)C[SiH2]C(OCC)OCC IFAPXTBWPQMLAF-UHFFFAOYSA-N 0.000 description 2
- LOOUJXUUGIUEBC-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propane-1-thiol Chemical compound COC(OC)[SiH2]CCCS LOOUJXUUGIUEBC-UHFFFAOYSA-N 0.000 description 2
- XRRIEVLGJHESLO-UHFFFAOYSA-N 3-[3-(2-methoxyethoxy)propoxysilyl]propane-1-thiol Chemical compound COCCOCCCO[SiH2]CCCS XRRIEVLGJHESLO-UHFFFAOYSA-N 0.000 description 2
- JNIZBWHSLQTTSB-UHFFFAOYSA-N 3-[cyclohexyloxy(dimethyl)silyl]propane-1-thiol Chemical compound SCCC[Si](C)(C)OC1CCCCC1 JNIZBWHSLQTTSB-UHFFFAOYSA-N 0.000 description 2
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 2
- XDFJBMAPHNLKKR-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]-n-ethyl-2-methylpropan-1-amine Chemical compound CCNCC(C)C[Si](C)(OC)OC XDFJBMAPHNLKKR-UHFFFAOYSA-N 0.000 description 2
- GRAYHTCZJNBKRL-UHFFFAOYSA-N 3-[dimethoxy(phenyl)silyl]-2-methylpropane-1-thiol Chemical compound SCC(C)C[Si](OC)(OC)C1=CC=CC=C1 GRAYHTCZJNBKRL-UHFFFAOYSA-N 0.000 description 2
- CLHDHUPZLNNYCB-UHFFFAOYSA-N 3-[dimethoxy(phenyl)silyl]oxypropane-1-thiol Chemical compound SCCCO[Si](OC)(OC)C1=CC=CC=C1 CLHDHUPZLNNYCB-UHFFFAOYSA-N 0.000 description 2
- QJMDSXQFYPCDDR-UHFFFAOYSA-N 3-[dimethoxy-(2-methylphenyl)silyl]oxypropane-1-thiol Chemical compound SCCCO[Si](OC)(OC)C1=CC=CC=C1C QJMDSXQFYPCDDR-UHFFFAOYSA-N 0.000 description 2
- FMRSVUHIKQTOFR-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(C)CCCS FMRSVUHIKQTOFR-UHFFFAOYSA-N 0.000 description 2
- DQMRXALBJIVORP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(C)CCCS DQMRXALBJIVORP-UHFFFAOYSA-N 0.000 description 2
- LQMCVFDSKWCIGP-UHFFFAOYSA-N 3-[tris[(2-methylpropan-2-yl)oxy]silyl]propane-1-thiol Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCCS LQMCVFDSKWCIGP-UHFFFAOYSA-N 0.000 description 2
- CJUFQURUUZMUOG-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropane-1-thiol Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCS CJUFQURUUZMUOG-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- QSUKAUDXXCSABB-UHFFFAOYSA-N 3-trimethoxysilylcyclohexane-1-thiol Chemical compound CO[Si](OC)(OC)C1CCCC(S)C1 QSUKAUDXXCSABB-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- WEPFXPXOMFVBDZ-UHFFFAOYSA-N 3-trioctoxysilylpropane-1-thiol Chemical compound CCCCCCCCO[Si](CCCS)(OCCCCCCCC)OCCCCCCCC WEPFXPXOMFVBDZ-UHFFFAOYSA-N 0.000 description 2
- KNYSNQHOKNRINQ-UHFFFAOYSA-N 4-(dimethoxymethylsilyl)-N-ethyl-2,2-dimethylbutan-1-amine Chemical compound CCNCC(C)(C)CC[SiH2]C(OC)OC KNYSNQHOKNRINQ-UHFFFAOYSA-N 0.000 description 2
- VZOYYUCUWMWSIK-UHFFFAOYSA-N 4-[diethoxy-(2-methylphenyl)silyl]oxybutane-1-thiol Chemical compound SCCCCO[Si](OCC)(OCC)C1=CC=CC=C1C VZOYYUCUWMWSIK-UHFFFAOYSA-N 0.000 description 2
- MPGJPVZZFPGZQG-UHFFFAOYSA-N 4-[dimethoxy(phenyl)silyl]oxybutane-1-thiol Chemical compound SCCCCO[Si](OC)(OC)C1=CC=CC=C1 MPGJPVZZFPGZQG-UHFFFAOYSA-N 0.000 description 2
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 description 2
- LMAFAQBMCIYHQS-UHFFFAOYSA-N 4-trimethoxysilylbutane-1-thiol Chemical compound CO[Si](OC)(OC)CCCCS LMAFAQBMCIYHQS-UHFFFAOYSA-N 0.000 description 2
- ZWLDNGJSJBLBFK-UHFFFAOYSA-N 4-trimethoxysilylbutane-2-thiol Chemical compound CO[Si](OC)(OC)CCC(C)S ZWLDNGJSJBLBFK-UHFFFAOYSA-N 0.000 description 2
- HIVACBGNJINCKA-UHFFFAOYSA-N 4-tripropoxysilylbutane-2-thiol Chemical compound CCCO[Si](CCC(C)S)(OCCC)OCCC HIVACBGNJINCKA-UHFFFAOYSA-N 0.000 description 2
- KVSQEHYSGZHEJQ-UHFFFAOYSA-N 5-[diethoxy(phenyl)silyl]oxypentane-1-thiol Chemical compound SCCCCCO[Si](OCC)(OCC)C1=CC=CC=C1 KVSQEHYSGZHEJQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- SMIDUPHNWFRONB-UHFFFAOYSA-N n,2-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CNCC(C)C[Si](OC)(OC)OC SMIDUPHNWFRONB-UHFFFAOYSA-N 0.000 description 2
- KGNDVXPHQJMHLX-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CCCNC1CCCCC1 KGNDVXPHQJMHLX-UHFFFAOYSA-N 0.000 description 2
- SWPRLROHVKTMPN-UHFFFAOYSA-N n-butyl-2-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CCCCNCC(C)C[Si](OC)(OC)OC SWPRLROHVKTMPN-UHFFFAOYSA-N 0.000 description 2
- YJOGKUUQSLYPQJ-UHFFFAOYSA-N n-ethyl-2,2-dimethyl-4-trimethoxysilylbutan-1-amine Chemical compound CCNCC(C)(C)CC[Si](OC)(OC)OC YJOGKUUQSLYPQJ-UHFFFAOYSA-N 0.000 description 2
- PNAUMDBGSPRGCS-UHFFFAOYSA-N n-ethyl-2-methyl-3-triethoxysilylpropan-1-amine Chemical compound CCNCC(C)C[Si](OCC)(OCC)OCC PNAUMDBGSPRGCS-UHFFFAOYSA-N 0.000 description 2
- OKIKLSJWTXOVSF-UHFFFAOYSA-N n-methyl-2-(3-trimethoxysilylpropoxy)propan-1-amine Chemical compound CNCC(C)OCCC[Si](OC)(OC)OC OKIKLSJWTXOVSF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- CGLQOIMEUPORRI-UHFFFAOYSA-N 2-(1-benzoyloxypropan-2-yloxy)propyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)OC(C)COC(=O)C1=CC=CC=C1 CGLQOIMEUPORRI-UHFFFAOYSA-N 0.000 description 1
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical class C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical group C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- WCLDITPGPXSPGV-UHFFFAOYSA-N tricamba Chemical compound COC1=C(Cl)C=C(Cl)C(Cl)=C1C(O)=O WCLDITPGPXSPGV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Definitions
- This invention relates to silylated polymers and to pressure sensitive adhesive (PSA) compositions containing same.
- solvent-resistant adhesives are also required for labels used by analytical laboratories such as environmental and medical laboratories to prevent loss of critical sample identification information. Further applications include electronic labels or masked areas undergoing further processes; dry cleaning labels for garments; degreasing operations where identification labels or masked-off areas are required, and the like. Adhesive properties of many pressure sensitive or heat-activated adhesives are well suited for use with labels on various substrates. However, these are not significantly solvent-resistant and therefore it is highly desirable that a solvent-resistant adhesive be provided.
- Solvent-resistant adhesive compositions are known in the art.
- JP 56082863 describes a thermoplastic polystyrene-polybutadiene block copolymer or a mixture thereof with another thermoplastic rubber of ethylene-vinyl acetate copolymer combined with an acryl-modified polybutadiene.
- JP 57207663 describes a compound comprised of ethylenic ionomer resin, a polyurethane resin, a polyethylene resin, a polyamide resin, a polyester resin, an agent for the thermal curing of a synthetic resin, and a thickener.
- JP 59172575 describes a solvent-resistant hot melt adhesive comprised of a polyester amide containing terminal alkoxyl groups prepared by reacting an aminoalkylalkoxysilane compound with a polyester-amide containing terminal isocyanate groups.
- JP 59174672 describes a solvent-resistant acrylic adhesive comprised of the reaction product a vinyl compound (e.g., methyl acrylate, isobutyl methacrylate, etc.) and a vinyl dioxazolone compound.
- a vinyl compound e.g., methyl acrylate, isobutyl methacrylate, etc.
- a vinyl dioxazolone compound e.g., methyl acrylate, isobutyl methacrylate, etc.
- JP 61047774 describes a solvent-resistant adhesive comprised of amino group terminated polyamide resin reacted with a isocyanate group-containing alkoxysilane that is the addition product of, for example, hexamethylene diisocyanate and 3-aminopropyltriethoxy-silane.
- JP 61218631 describes a solvent-resistant adhesive comprised of a silane-modified polyester resin obtained by reacting a polyester resin containing a hydroxyl group with an isocyanate group-containing hydrolyzable organosilicon compound.
- JP 61218672 describes a solvent-resistant acrylic adhesive comprised of an unsaturated polyester resin having terminal ethylenic groups which is the reaction product of a ethylenic compound having isocyanate groups with terminal hydroxyl groups or carboxyl groups of an unsaturated polyester resin.
- JP 61218673 describes a solvent-resistant acrylic adhesive comprised of an unsaturated polyester resin having terminal ethylenic double bonds obtained by reacting epoxy (meth)acrylate with the terminal carboxyl groups of an unsaturated polyester resin having ethylenic double bond in the molecule.
- JP 62057480 describes a solvent-resistant adhesive comprised of a polyamide resin having terminal ethylenic double bonds obtained by reacting a compound having aziridinyl and ethylenic groups with terminal carboxyl groups of a polyamide resin.
- JP 62057479 describes a solvent-resistant adhesive comprised of an unsaturated polyester resin having both terminal and in-chain ethylenic double bonds obtained by reacting a compound having aziridinyl and ethylenic groups with terminal carboxyl groups of an unsaturated polyester resin.
- JP 62057478 describes a solvent-resistant adhesive comprised of an unsaturated polyester resin having terminal and in-chain ethylenic double bonds obtained by reacting a terminal hydroxyl group of an unsaturated polyester resin with an epoxy (meth)acrylate.
- JP 62089782 describes a solvent-resistant adhesive obtained by reaction between a high-molecular weight diol, preferably a polyester diol of polyethylene-butylene- adipate, a divalent isocyanate compound, a chain extender and a hindered nitrogen atom compound such as one containing a piperizine ring.
- JP 03259981 describes a solvent-resistant adhesive comprised of a composition prepared by compounding a block copolymer and an isocyanate prepolymer.
- the block copolymer comprises a block consisting of at least two kinds of aromatic vinyl monomer and a block consisting of at least one kind of a conjugated diene monomer in which at least 50% of carbon- carbon double bonds in the block have been hydrogenated (e.g. a hydrogenated styrene-isoprene-styrene triblock copolymer).
- the isocyanate prepolymer is obtained by reacting an isocyanate compound with a liquid polymer which comprises a polymer of isoprene or isoprene-butadiene mixture and has 1.5-5.0 hydroxyl groups in the molecule and in which at least 50% of the carbon-carbon double bonds have been hydrogenated.
- JP 09165565 describes a solvent-resistant adhesive composition which is a blend of a base polymer with a tackifier resin and, optionally, a softening agent or a wax, a block copolymer which comprises one or more hydrogenated butadiene polymer blocks, one or more of aromatic vinyl compound polymer blocks and one or more polymer blocks substantially having an olefin polymer structure.
- a silylated polymer containing repeating units derived from butadiene containing repeating units derived from butadiene.
- a moisture-curable pressure sensitive adhesive composition of improved solvent resistance comprising partially silylated polymer containing repeating units derived from butadiene and, optionally, one or more known or conventional adhesive composition additives.
- the silylated polymer of this invention is derived from hydroxyl-terminated polybutadiene, understood herein to include any hydroxyl-terminated polymer in which at least about 50 weight percent of the polymer is made up of units derived from butadiene.
- the silylated polymer is obtained (1) by the silylation (i.e., end capping) of polybutadiene-based polyurethane prepolymer possessing isocyanate termination with a silane possessing at least one hydrolyzable group and functionality which is reactive for isocyanate, e.g., a secondary aminoalkyltrialkoxysilane, or (2) by the silylation of a polybutadiene-based polyurethane prepolymer possessing hydroxyl termination with an isocyanatosilane possessing at least one hydrolyzable group.
- the polybutadiene-based polyurethane prepolymer is obtained by reacting one or more hydroxyl-terminated, optionally hydrogenated, linear or branched polybutadiene homopolymers or copolymers with an organic polyisocyanate, e.g., an organic diisocyanate, optionally together with one or more other difunctional compounds and/or hydroxyl-terminated polymers, to provide (1) an isocyanate-terminated polyurethane prepolymer when the total equivalents of isocyanate functionality exceeds the total equivalents of hydroxyl functionality, and (2) a hydroxyl-terminated polyurethane prepolymer when the total equivalents of hydroxyl functionality exceeds the total equivalents of isocyanate functionality.
- an organic polyisocyanate e.g., an organic diisocyanate
- Mn number average molecular weight
- Hydroxyl-terminated butadienes of the above-described type averaging more than one predominantly primary hydroxyl group per molecule, e.g., averaging from about 1.7 to about 3 or more primary hydroxyl groups per molecule, are suitably employed herein.
- the hydroxyl-terminated polybutadienes will possess an average of at least about 2, and advantageously from about 2.4 up to about 2.8, hydroxyl groups per molecule, the hydroxyl groups being predominantly in terminal allylic positions on the main, i.e., generally longest, hydrocarbon chain of the molecule.
- allylic configuration is meant that the alpha-allylic grouping of allylic alcohol, i.e., the terminal hydroxyl groups of the polymer, are bonded to carbon atoms adjacent to double bonded carbon atoms.
- the ratio of cis-1,4, trans-1,4 and 1,2-vinyl unsaturation which occurs in the butadiene polymers employed in this invention, the number and location of the hydroxyl groups and the molecular weight of the butadiene polymers will be influenced by the process employed for their manufacture, the details of which are known in the art.
- Hydroxyl-terminated polybutadienes possessing these characteristics are commercially available from several sources and are therefore conveniently employed herein.
- the useful hydroxyl-terminated polybutadienes herein can also incorporate one or more other copolymerizable monomers which can confer particularly desirable properties upon the silylated polymers herein and the pressure sensitive adhesive compositions prepared therewith.
- the total amount of copolymerized monomer will not exceed, on average, 50 weight percent of the hydroxyl-terminated polybutadiene copolymer.
- the copolymerizable monomers include monoolefins and dienes such as ethylene, propylene, 1-butene, isoprene, chloroprene, 2,3-methyl-1,3-butadiene, 1,4-pentadiene, etc., and, ethylenically unsaturated monomers such as acrylonitrile, methacrylonitrile, methylstyrene, methyl acrylate, methyl methacrylate, vinyl acetate, etc.
- the hydroxyl-terminated polybutadienes can be reacted with one or more other monomers to provide hydroxyl-terminated block copolymers.
- Such monomers include 1,2-epoxides such as ethylene oxide and propylene oxide which will provide polyether segments, e-caprolactone which will provide polyester segments, and the like.
- Isocyanate-terminated polyurethane prepolymers useful in the present invention, are prepared by reacting an excess of organic polyisocyanate with one or more of the foregoing hydroxyl-terminated polybutadiene homopolymers and or copolymers, generally, in the presence of a catalyst.
- polyisocyanate means an organic compound possessing two or more isocyanate groups.
- the reaction temperature is typically in the range of from about 60° to about 90° C.; the reaction time is typically from about 4 to about 8 hours.
- the reaction mixture can contain one or more chain extenders and/or one or more other polyols.
- suitable chain extenders are polyhydric alcohols such as ethylene glycol, propylene glycol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, triethylene glycol, tetrathylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and the like.
- Additional polyols include polyether polyols, polyester polyols, polyetherester polyols, polyesterether polyols, polybutadienediols, polyoxyalkylene diols, polyoxyalkylene triols, polytetramethylene glycols, polycaprolactone diols and triols, and the like, all of which possess at least two primary hydroxyl groups.
- Suitable organic polyisocyanates include any of the known and conventional organic polyisocyanates, especially organic diisocyanates, from which polyurethane polymers have heretofore been prepared.
- Useful diisocyanates include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4' diphenyl-methanediisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, various liquid diphenylmethane-diisocyantes containing a mixture of 2,4- and 4,4' isomers, Desmodur N® (Bayer) and the like, and mixtures thereof.
- Isophorone diisocyanate is especially advantageous for use in preparing the polyurethane prepolymers herein.
- Suitable catalysts useful in the preparation of the polyurethane prepolymers are dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltin acetate, tertiary amines, the stannous salts of carboxylic acids such as stannous octoate and stannous acetate, and the like.
- isocyanate-terminated polyurethane prepolymers To prepare isocyanate-terminated polyurethane prepolymers, at least a slight mole excess of the isocyanate equivalents (NCO groups) with respect to the hydroxyl equivalents (OH groups) is employed to terminate the polybutadiene homopolymer(s) and/or copolymer(s) with isocyanate groups.
- the molar ratio of NCO to OH is from about 1.1 to about 4.0 depending on the selection of the particular hydroxyl-terminated polybutadiene homopolymer(s) and/or copolymer(s), optional chain extenders and optional non-butadiene based polyols.
- Hydroxyl-terminated polyurethane prepolymers useful in the present invention, can be prepared by the reaction of an organic polyisocyanate, e.g., a diisocyanate such as any of those mentioned above, and advantageously isophorone diisocyanate, with a stoichiometric excess of the selected hydroxyl-terminated polybutadiene homopolymer(s) and/or copolymer(s).
- a catalyst such as any of those mentioned above can be employed.
- the reaction temperature is typically in the range of from about 60° to about 90° C.; the reaction time is typically on the order of from about 2 to about 8 hours.
- the reaction mixture can also contain one or more chain extenders and/or other polyols such as any of those mentioned above.
- the hydroxyl group-terminated polyurethane prepolymers To prepare the hydroxyl group-terminated polyurethane prepolymers, at least a slight molar excess of the hydroxyl equivalents (OH groups) with respect to the NCO isocyanate equivalents (NCO groups) is employed to terminate the polybutadiene chains with hydroxyl groups.
- the molar ratio of NCO to OH is from about 0.3 to about 0.95, and more preferably from about 0.5 to about 0.90, depending on the specific hydroxyl-terminated polybutadiene employed.
- Silylation of the isocyanate-terminated polyurethane prepolymer can be accomplished by reacting the prepolymer with a silane possessing at least one hydrolyzable group and at least one functionality which is reactive for isocyanate, i.e., an active hydrogen-containing group such as hydroxyl, carboxylic acid, mercapto, primary amino or secondary amino.
- a silane possessing at least one hydrolyzable group and at least one functionality which is reactive for isocyanate i.e., an active hydrogen-containing group such as hydroxyl, carboxylic acid, mercapto, primary amino or secondary amino.
- the silane is a primary or secondary aminosilane of the general formula: X - R 1 - Si(R 2 ) x (OR 3 ) 3-x wherein X is an active hydrogen-containing group that is reactive for isocyanate, e.g., -SH or -NHR 4 in which R 4 is H, a monovalent hydrocarbon group of up to 8 carbon atoms or -R 5 -Si(R 6 ) y (OR 7 ) 3-y , R 1 and R 5 each is the same or different divalent hydrocarbon group of up to 12 carbon atoms, optionally containing one or more heteroatoms, each R 2 and R 6 is the same or different monovalent hydrocarbon group of up to 8 carbon atoms, each R 3 and R 7 is the same or different alkyl group of up to 6 carbon atoms and x and y each, independently, is 0, 1 or 2.
- X is an active hydrogen-containing group that is reactive for isocyanate, e.g., -SH or -
- Non-limiting examples of aminosilanes for use in the silylation procedure herein include the mercaptosilanes 2-mercaptoethyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 2-mercaptopropyl triethoxysilane, 3 -mercaptopropyl triethoxysilane, 2-mercaptoethyl tripropoxysilane, 2-mercaptoethyl tri sec-butoxysilane, 3-mercaptopropyl tri-t-butoxysilane, 3-mercaptopropyl triisopropoxysilane, 3-mercaptopropyl trioctoxysilane, 2-mercaptoethyl tri-2'-ethylhexoxysilane, 2-mercaptoethyl dimethoxy ethoxysilane, 3-mercaptopropyl methoxyethoxypropoxysilane, 3-mercaptopropyl dimethoxy methylsilane, 3-mer
- the polyurethane prepolymers can be substantially fully silylated, i.e., all, or substantially all, of the isocyanate groups can be reacted with silane to provide a completely silylated polyurethane polymer.
- silylated polyurethane polymer is to be incorporated into pressure sensitive adhesive compositions, it is important that the silylation be conducted to less than completion in order that the extent of crosslinking that occurs on subsequent cure of the silylated polymer not be so great as to adversely affect, and even eliminate, the pressure sensitive adhesive characteristics of the crosslinked polymer.
- silane and optional amine for achieving this less-than-complete silylation operation can be readily determined for a given isocyanate-terminated prepolymer employing known and conventional experimental techniques. Silylation of not more than about 95 percent, and advantageously not more than about 90 percent, of the total isocyanate groups present in the prepolymer is generally suitable for most pressure sensitive adhesive applications.
- Silylation of the hydroxyl-terminated polyurethane prepolymer can be accomplished by reacting the prepolymer with an isocyanatosilane.
- Suitable isocyanatosilanes are those of the general formula: wherein R 1 is a divalent alkylene group of from 3 to 10 carbon atoms, R 2 and R 3 each independently is an alkyl group of from 1 to 6 carbon atoms or an aryl group of from 6 to 8 carbon atoms, and x has a value of 0, 1 or 2.
- isocyanatosilanes for use in the silylation procedure are ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxy-silane, ⁇ -isocyanatomethylpropyltrimethoxysilane, ⁇ -isocyanatomethylpropyltriethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatopropyldimethylmethoxysilane and ⁇ -isocyanatomethylpropyldimethylmethoxysilane.
- the silylation of the hydroxyl-terminated polyurethane prepolymers herein will be substantially complete, i.e., essentially no hydroxyl groups will be present following silylation, where the silylated polymers are to be incorporated in such products as sealants and coatings.
- silylation will be incomplete, or partial, where the silylated polymers are to be incorporated in pressure sensitive adhesive compositions.
- levels of silylation of not more than about 95 percent, and advantageously, not more than about 90 percent, of the total hydroxyl groups present in the prepolymer is generally suitable and can be achieved by appropriate adjustment of the amounts of isocyanatosilane being reacted for a given prepolymer.
- a hydroxyl-reactive monofunctional reactant with the isocyanatosilane.
- Suitable reactants for this purpose include monoisocyanates such as n-butylisocyanate. These and similar reactants serve to cap some of the hydroxyl groups of the prepolymer preventing them from undergoing silylation. Amounts of such hydroxyl-reactive monomeric reactants and isocyanatosilanes that can be utilized for partial silylation herein can be readily determined for a specific hydroxyl-terminated polyuretehane prepolymer employing routine experimental testing.
- a solvent-resistant pressure sensitive adhesive composition in accordance with the invention will typically include one or more additives such as fillers, tackifiers, silane adhesion promoters, plasticizers, solvents, thixotropic agents, U.V. stabilizers, antioxidants, cure catalysts, etc., in the usual amounts.
- Typical fillers suitable for addition to the pressure-sensitive adhesive compositions of this invention include fumed silica, precipitated silica and calcium carbonates. Treated calcium carbonates having particle sizes from about 0.07 ⁇ to about 4 ⁇ are particularly useful and are available under several trade names: Ultra Pflex, Super Pflex, Hi Pflex from Specialty in Minerals; Winnofil SPM, SPT from Zeneca Resins; Hubercarb lat, Hubercarb 3Qt and Hubercarb W from Huber and Kotomite from ECC. These fillers can be used either alone or in combination.
- the fillers can comprise up to about 200 parts per 100 parts of the silylated polymer component(s) with from about 80 to about 150 parts filler per 100 parts polymer being suitable for many adhesive applications.
- the pressure sensitive adhesive composition can contain from about 20 to about 60 parts, and advantageously from about 30 to about 50 parts, of one or more known of conventional tackifiers per 100 parts of silylated polyurethane polymer.
- suitable tackifiers are MQ silicone resins (for which a curing catalyst such as benzoyl peroxide will ordinarily be included), terpene oligomers, coumarone/indene resins, aliphatic, petrochemical resins, and modified phenolic resins.
- Silane adhesion promoters can be employed at levels of from about 0.5 to about 5 parts per hundred parts of the silylated polyurethane polymer with from about 0.8 to about 1.5 parts per hundred parts polymer being especially advantageous.
- Suitable adhesion promoters include Silquest A-1120 silane, Silquest A-2120 silane, Silquest A-1170 silane and Silquest A-187 silane, all of which are available from GE Silicones.
- Exemplary plasticizers include phthalates, dipropylene and diethylene glycol dibenzoates and mixtures thereof, epoxidized soybean oil, and the like.
- Dioctyl and diisodecylphthalate are commercially available under the trade names Jayflex DOP and JayFlex DIDP from Exxon Chemical.
- the dibenzoates are available as Benzoflex 9-88, Benzoflex 50 and Benzoflex 400 from Velsicol Chemical Corporation.
- Epoxidized soybean oil is available from Houghton Chemical Corporation as Flexol EPO.
- the plasticizer can comprise up to about 100 parts of the silylated polyurethane polymer with from about 40 to about 80 parts per hundred parts of silylated polymer being satisfactory in many cases.
- Useful solvents include aromatic, aliphatic and esters ranging in amounts of from about 25 to about 75 per hundred parts by weight of silylated polyurethane prepolymer.
- thixotropic agents are various castor waxes, fumed silica, treated clays and polyamides. These additives typically comprise about 1 to about 10 parts per hundred parts of silylated polyurethane prepolymer with from about 1 to about 6 parts being useful for most applications.
- the thixotropes include those available as: Aerosil from Degussa, Cabo-Sil TS 720 from Cabot, Castorwax from CasChem, Thixatrol and Thixcin from Rheox and Dislon from King Industries. If the thixotrope is reactive with silane (e.g., silica), adjustments to the amount formulated may be needed to compensate therefor.
- U. V. stabilizers and/or antioxidants can be incorporated into the pressure sensitive adhesive compositions of this invention in an amount of from 0 to about 5 parts per hundred parts silylated polyurethane polymer with from about 0.5 to about 2 parts providing generally good results.
- These materials are available from Ciba-Geigy under the trade names Tinuvin 770, Tinuvin 327, Tinuvin 213, Tinuvin 622 and Irganox 1010.
- Suitable cure catalysts are the same as those previously described for preparation of the silylated polyurethane polymers.
- the catalysts typically compromise from about 0.01 to about 3 parts per hundred parts polymer with from about 0.01 to about 1.0 parts per hundred parts of polymer being entirely suitable in many cases.
- the pressure sensitive adhesive compositions are cured by exposure to moisture.
- Curing conditions typically include ambient temperature, e.g., about 23° C. and 50% relative humidity for 3 days and 37° C. and 95% relative humidity for another 4 days.
- water can be dissolved in an appropriate solvent such as isopropanol followed by mixing with the adhesive composition and coated, cured in convensional adhesive cure ovens known in the art.
- Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto a smooth surface Delrin® (DuPont's polyoxymethylene) plaque with a 100 g weight.
- the lap shear samples were suspended in xylene that was slowly stirred using a magnetic stirrer and bar. Testing was conducted in duplicate and times to adhesive failure were 200 and 165 minutes.
- This reaction product was blended 1:1 on a weight basis with Norsolene A-110 (SpecialChem) resin then cured using 1 wt% benzoyl peroxide for 5 minutes at 130° C. Time to failure was 210 minutes for the Delrin® substrate.
- Example 1 The temperature was reduced to 65 °C and 8.0 g 3-isocyanatopropyltrimethoxysilane was added and further heated at 70-80 °C for 4 hours. A sample was coated and cured as in Example 1 and time to adhesive failure on a smooth surface Delrin® plaque was found to be 70 and 75 minutes and on glass slides 40 and 60 minutes.
- silylated polymers prepared from hydroxyl-terminated polybutadienes of different number average molecular weights, blends of hydroxyl-terminated polybutadienes, various NCO/OH ratios for preparing the polyurethane prepolymers and pressure sensitive adhesive compositions containing the silylated polymers and optional tackifier.
- Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto 1 minute preheated at 135 °C to a smooth surface Delrin® plaque and a glass slide with a 100 g weight attached to the opposite end.
- the lap shear samples were suspended in xylene that was slowly stirred using a magnetic stirrer and bar. Times to adhesive failure are set forth in Table 1 below.
- a second sample without benzoyl peroxide was also coated. All samples were bar-coated onto a 2 mil polyester film to yield an approximately 1 mil dry adhesive thickness, air-dried 10 minutes then cured for 5 minutes at 150 °C. Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto a textured surface Delrin cassette and a glass slide with a 10 g weight attached to the opposite end. Time to adhesive failure for the benzoyl peroxide cured adhesive coating was 40 minutes for the cassette and 2 hours for the glass slide. The sample without benzoyl peroxide resulted in adhesive failure in 2 hours for the cassette and 2.5 hours for the glass slide.
- This example illustrates hydrosilylation crosslinking of silylated polyurethane polymer.
- the coated sample was bar-coated onto a 2 mil polyester film to yield an approximate 1 mil dry adhesive thickness, air-dried 10 minutes then cured for 5 minutes at 150 °C.
- Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto a textured surface Delrin® cassette with a 10 g weight attached to the opposite end. Time to adhesive failure was 3.5 hours.
- This example illustrates the silylation of an hydroxyl terminated polyurethane prepolymer with an isocyanato silane capping agent.
- a 25 g sample was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness.
- the adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C.
- Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved.
- Shear adhesion failure temperature (SAFT) for 1.0 inch x 1.0 inch overlap and 1 Kg weight was determined to be 275 °C.
- SAFT Shear adhesion failure temperature
- This comparative example is similar to Example 40 except that the polyurethane prepolymer was not silylated.
- a 25 g sample was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness.
- the adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C.
- Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved.
- SAFT Shear adhesion failure temperature
- a 25 g sample of this composition was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness.
- the adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C.
- Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved.
- Shear adhesion failure temperature (SAFT) for 1.0 inch x 1.0 inch overlap and 1 Kg weight was determined to be greater than 281°C.
- SAFT Shear adhesion failure temperature
- This comparative example is similar to Example 42 except that the polyurethane prepolymer was not silylated.
- a 25 g sample was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness.
- the adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C.
- Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved.
- Shear adhesion failure temperature (SAFT) for 1.0 inch x 1.0 inch overlap and 1 Kg weight was determined to be 62 °C.
- SAFT Shear adhesion failure temperature
- the present invention generally relates to the following aspects:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
- The present application is a continuation in part of U.S. application Serial No.
11/119,263 filed April 29, 2005 - This invention relates to silylated polymers and to pressure sensitive adhesive (PSA) compositions containing same.
- There are certain adhesive applications for which solvent resistance is highly desirable. These include automotive, aerospace, industrial and consumer labels where exposure to aromatic, aliphatic solvents and oils occurs. Solvent-resistant adhesives are also required for labels used by analytical laboratories such as environmental and medical laboratories to prevent loss of critical sample identification information. Further applications include electronic labels or masked areas undergoing further processes; dry cleaning labels for garments; degreasing operations where identification labels or masked-off areas are required, and the like. Adhesive properties of many pressure sensitive or heat-activated adhesives are well suited for use with labels on various substrates. However, these are not significantly solvent-resistant and therefore it is highly desirable that a solvent-resistant adhesive be provided.
- Solvent-resistant adhesive compositions are known in the art.
-
JP 56082863 -
JP 57207663 -
JP 59172575 -
JP 59174672 -
JP 61047774 -
JP 61218631 -
JP 61218672 -
JP 61218673 -
JP 62057480 -
JP 62057479 -
JP 62057478 -
JP 62089782 -
JP 03259981 -
JP 09165565 - In accordance with the present invention, there is provided a silylated polymer containing repeating units derived from butadiene.
- Further in accordance with the invention herein, there is provided a moisture-curable pressure sensitive adhesive composition of improved solvent resistance comprising partially silylated polymer containing repeating units derived from butadiene and, optionally, one or more known or conventional adhesive composition additives.
- The silylated polymer of this invention is derived from hydroxyl-terminated polybutadiene, understood herein to include any hydroxyl-terminated polymer in which at least about 50 weight percent of the polymer is made up of units derived from butadiene.
- The silylated polymer is obtained (1) by the silylation (i.e., end capping) of polybutadiene-based polyurethane prepolymer possessing isocyanate termination with a silane possessing at least one hydrolyzable group and functionality which is reactive for isocyanate, e.g., a secondary aminoalkyltrialkoxysilane, or (2) by the silylation of a polybutadiene-based polyurethane prepolymer possessing hydroxyl termination with an isocyanatosilane possessing at least one hydrolyzable group.
- The polybutadiene-based polyurethane prepolymer is obtained by reacting one or more hydroxyl-terminated, optionally hydrogenated, linear or branched polybutadiene homopolymers or copolymers with an organic polyisocyanate, e.g., an organic diisocyanate, optionally together with one or more other difunctional compounds and/or hydroxyl-terminated polymers, to provide (1) an isocyanate-terminated polyurethane prepolymer when the total equivalents of isocyanate functionality exceeds the total equivalents of hydroxyl functionality, and (2) a hydroxyl-terminated polyurethane prepolymer when the total equivalents of hydroxyl functionality exceeds the total equivalents of isocyanate functionality.
- Among the hydroxyl-terminated polybutadienes that are useful for preparing the isocyanate-terminated and hydroxyl-terminated polyurethane prepolymers are those possessing a number average molecular weight (Mn) of from about 500 to about 10,000, and advantageously from about 800 to about 5,000, a primary hydroxyl group content of from about 0.1 to about 2.0 meq/g, and advantageously from about 0.3 to about 1.8 meq/g, a degree of hydrogenation of from 0 up to 100 percent of the olefinic sites present and an average content of copolymerized additional monomer(s) of from 0 up to about 50 weight percent.
- Hydroxyl-terminated butadienes of the above-described type, averaging more than one predominantly primary hydroxyl group per molecule, e.g., averaging from about 1.7 to about 3 or more primary hydroxyl groups per molecule, are suitably employed herein. The hydroxyl-terminated polybutadienes will possess an average of at least about 2, and advantageously from about 2.4 up to about 2.8, hydroxyl groups per molecule, the hydroxyl groups being predominantly in terminal allylic positions on the main, i.e., generally longest, hydrocarbon chain of the molecule. By "allylic" configuration is meant that the alpha-allylic grouping of allylic alcohol, i.e., the terminal hydroxyl groups of the polymer, are bonded to carbon atoms adjacent to double bonded carbon atoms.
- The ratio of cis-1,4, trans-1,4 and 1,2-vinyl unsaturation which occurs in the butadiene polymers employed in this invention, the number and location of the hydroxyl groups and the molecular weight of the butadiene polymers will be influenced by the process employed for their manufacture, the details of which are known in the art.
- Hydroxyl-terminated polybutadienes possessing these characteristics are commercially available from several sources and are therefore conveniently employed herein.
- The useful hydroxyl-terminated polybutadienes herein can also incorporate one or more other copolymerizable monomers which can confer particularly desirable properties upon the silylated polymers herein and the pressure sensitive adhesive compositions prepared therewith. The total amount of copolymerized monomer will not exceed, on average, 50 weight percent of the hydroxyl-terminated polybutadiene copolymer. Included among the copolymerizable monomers are monoolefins and dienes such as ethylene, propylene, 1-butene, isoprene, chloroprene, 2,3-methyl-1,3-butadiene, 1,4-pentadiene, etc., and, ethylenically unsaturated monomers such as acrylonitrile, methacrylonitrile, methylstyrene, methyl acrylate, methyl methacrylate, vinyl acetate, etc. Alternatively or in addition thereto, the hydroxyl-terminated polybutadienes can be reacted with one or more other monomers to provide hydroxyl-terminated block copolymers. Such monomers include 1,2-epoxides such as ethylene oxide and propylene oxide which will provide polyether segments, e-caprolactone which will provide polyester segments, and the like.
- Isocyanate-terminated polyurethane prepolymers, useful in the present invention, are prepared by reacting an excess of organic polyisocyanate with one or more of the foregoing hydroxyl-terminated polybutadiene homopolymers and or copolymers, generally, in the presence of a catalyst. As used herein, the term "polyisocyanate" means an organic compound possessing two or more isocyanate groups. The reaction temperature is typically in the range of from about 60° to about 90° C.; the reaction time is typically from about 4 to about 8 hours.
- In addition to the hydroxyl-terminated butadiene-based polymer, the reaction mixture can contain one or more chain extenders and/or one or more other polyols. Examples of suitable chain extenders are polyhydric alcohols such as ethylene glycol, propylene glycol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, triethylene glycol, tetrathylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and the like. Additional polyols include polyether polyols, polyester polyols, polyetherester polyols, polyesterether polyols, polybutadienediols, polyoxyalkylene diols, polyoxyalkylene triols, polytetramethylene glycols, polycaprolactone diols and triols, and the like, all of which possess at least two primary hydroxyl groups.
- Suitable organic polyisocyanates include any of the known and conventional organic polyisocyanates, especially organic diisocyanates, from which polyurethane polymers have heretofore been prepared. Useful diisocyanates include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4' diphenyl-methanediisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, various liquid diphenylmethane-diisocyantes containing a mixture of 2,4- and 4,4' isomers, Desmodur N® (Bayer) and the like, and mixtures thereof. Isophorone diisocyanate is especially advantageous for use in preparing the polyurethane prepolymers herein.
- Suitable catalysts useful in the preparation of the polyurethane prepolymers are dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltin acetate, tertiary amines, the stannous salts of carboxylic acids such as stannous octoate and stannous acetate, and the like.
- To prepare isocyanate-terminated polyurethane prepolymers, at least a slight mole excess of the isocyanate equivalents (NCO groups) with respect to the hydroxyl equivalents (OH groups) is employed to terminate the polybutadiene homopolymer(s) and/or copolymer(s) with isocyanate groups. Advantageously, the molar ratio of NCO to OH is from about 1.1 to about 4.0 depending on the selection of the particular hydroxyl-terminated polybutadiene homopolymer(s) and/or copolymer(s), optional chain extenders and optional non-butadiene based polyols.
- Hydroxyl-terminated polyurethane prepolymers, useful in the present invention, can be prepared by the reaction of an organic polyisocyanate, e.g., a diisocyanate such as any of those mentioned above, and advantageously isophorone diisocyanate, with a stoichiometric excess of the selected hydroxyl-terminated polybutadiene homopolymer(s) and/or copolymer(s). Depending on the reactivity of the respective reactants, a catalyst such as any of those mentioned above can be employed. The reaction temperature is typically in the range of from about 60° to about 90° C.; the reaction time is typically on the order of from about 2 to about 8 hours. The reaction mixture can also contain one or more chain extenders and/or other polyols such as any of those mentioned above.
- To prepare the hydroxyl group-terminated polyurethane prepolymers, at least a slight molar excess of the hydroxyl equivalents (OH groups) with respect to the NCO isocyanate equivalents (NCO groups) is employed to terminate the polybutadiene chains with hydroxyl groups. Advantageously, the molar ratio of NCO to OH is from about 0.3 to about 0.95, and more preferably from about 0.5 to about 0.90, depending on the specific hydroxyl-terminated polybutadiene employed.
- Silylation of the isocyanate-terminated polyurethane prepolymer can be accomplished by reacting the prepolymer with a silane possessing at least one hydrolyzable group and at least one functionality which is reactive for isocyanate, i.e., an active hydrogen-containing group such as hydroxyl, carboxylic acid, mercapto, primary amino or secondary amino. Advantageously, the silane is a primary or secondary aminosilane of the general formula:
X - R1 - Si(R2)x(OR3)3-x
wherein X is an active hydrogen-containing group that is reactive for isocyanate, e.g., -SH or -NHR4 in which R4 is H, a monovalent hydrocarbon group of up to 8 carbon atoms or -R5-Si(R6)y(OR7)3-y, R1 and R5 each is the same or different divalent hydrocarbon group of up to 12 carbon atoms, optionally containing one or more heteroatoms, each R2 and R6 is the same or different monovalent hydrocarbon group of up to 8 carbon atoms, each R3 and R7 is the same or different alkyl group of up to 6 carbon atoms and x and y each, independently, is 0, 1 or 2. - Non-limiting examples of aminosilanes for use in the silylation procedure herein include the mercaptosilanes 2-mercaptoethyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 2-mercaptopropyl triethoxysilane, 3 -mercaptopropyl triethoxysilane, 2-mercaptoethyl tripropoxysilane, 2-mercaptoethyl tri sec-butoxysilane, 3-mercaptopropyl tri-t-butoxysilane, 3-mercaptopropyl triisopropoxysilane, 3-mercaptopropyl trioctoxysilane, 2-mercaptoethyl tri-2'-ethylhexoxysilane, 2-mercaptoethyl dimethoxy ethoxysilane, 3-mercaptopropyl methoxyethoxypropoxysilane, 3-mercaptopropyl dimethoxy methylsilane, 3-mercaptopropyl methoxy dimethylsilane, 3-mercaptopropyl ethoxy dimethylsilane, 3-mercaptopropyl diethoxy methylsilane, 3-mercaptopropyl cyclohexoxy dimethyl silane, 4-mercaptobutyl trimethoxysilane, 3-mercapto-3-methylpropyltrimethoxysilane, 3-mercapto-3-methylpropyl-tripropoxysilane, 3-mercapto-3-ethylpropyl-dimethoxy methylsilane, 3-mercapto-2-methylpropyl trimethoxysilane, 3-mercapto-2-methylpropyl dimethoxy phenylsilane, 3-mercaptocyclohexyl-trimethoxysilane, 12-mercaptododecyl trimethoxy silane, 12-mercaptododecyl triethoxy silane, 18-mercaptooctadecyl trimethoxysilane, 18-mercaptooctadecyl methoxydimethylsilane, 2-mercapto-2-methylethyl-tripropoxysilane, 2-mercapto-2-methylethyl-trioctoxysilane, 2-mercaptophenyl trimethoxysilane, 2-mercaptophenyl triethoxysilane, 2-mercaptotolyl trimethoxysilane, 2-mercaptotolyl triethoxysilane, 1-mercaptomethyltolyl trimethoxysilane, 1-mercaptomethyltolyl triethoxysilane, 2-mercaptoethylphenyl trimethoxysilane, 2-mercaptoethyiphenyl triethoxysilane, 2-mercaptoethyltolyl trimethoxysilane, 2-mercaptoethyltolyl triethoxysilane, 3-mercaptopropylphenyl trimethoxysilane and, 3-mercaptopropylphenyl triethoxysilane, and the aminosilanes 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxy-silane, N-methyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino-2-methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropyl-methyldimethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, 3-(N-methyl-2-amino-1-methyl-1-ethoxy)-propyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethyl-butyldimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyltrimethoxy-silane, N-(cyclohexyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy-silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, bis-(3-trimethoxysilyl-2-methylpropyl)amine and N-(3'-trimethoxysilylpropyl)-3-amino-2-methylpropyltri-methoxysilane.
- For applications such as use in sealant and coating compositions, the polyurethane prepolymers can be substantially fully silylated, i.e., all, or substantially all, of the isocyanate groups can be reacted with silane to provide a completely silylated polyurethane polymer.
- However, where the silylated polyurethane polymer is to be incorporated into pressure sensitive adhesive compositions, it is important that the silylation be conducted to less than completion in order that the extent of crosslinking that occurs on subsequent cure of the silylated polymer not be so great as to adversely affect, and even eliminate, the pressure sensitive adhesive characteristics of the crosslinked polymer.
- In conducting a partial silylation reaction, it can be useful to include a primary monoamine such as N-ethylbutylamine or similar capping reactant together with the silane as the amine will readily end-cap isocyanate groups threreby precluding them from reacting with the silane. The optimal amounts of silane and optional amine for achieving this less-than-complete silylation operation can be readily determined for a given isocyanate-terminated prepolymer employing known and conventional experimental techniques. Silylation of not more than about 95 percent, and advantageously not more than about 90 percent, of the total isocyanate groups present in the prepolymer is generally suitable for most pressure sensitive adhesive applications.
- Silylation of the hydroxyl-terminated polyurethane prepolymer can be accomplished by reacting the prepolymer with an isocyanatosilane. Suitable isocyanatosilanes are those of the general formula:
- Examples of such isocyanatosilanes for use in the silylation procedure are λ-isocyanatopropyltrimethoxysilane, λ-isocyanatopropyltriethoxy-silane, λ-isocyanatomethylpropyltrimethoxysilane, λ-isocyanatomethylpropyltriethoxysilane, λ-isocyanatopropylmethyldimethoxysilane, λ-isocyanatopropyldimethylmethoxysilane and λ-isocyanatomethylpropyldimethylmethoxysilane.
- As in the case of the silylated isocyanate-terminated polyurethanes described above, the silylation of the hydroxyl-terminated polyurethane prepolymers herein will be substantially complete, i.e., essentially no hydroxyl groups will be present following silylation, where the silylated polymers are to be incorporated in such products as sealants and coatings. However, silylation will be incomplete, or partial, where the silylated polymers are to be incorporated in pressure sensitive adhesive compositions. In the case of incomplete silylation, levels of silylation of not more than about 95 percent, and advantageously, not more than about 90 percent, of the total hydroxyl groups present in the prepolymer is generally suitable and can be achieved by appropriate adjustment of the amounts of isocyanatosilane being reacted for a given prepolymer.
- In order to facilitate control over the extent of incomplete silylation, it may be advantageous to include a hydroxyl-reactive monofunctional reactant with the isocyanatosilane. Suitable reactants for this purpose include monoisocyanates such as n-butylisocyanate. These and similar reactants serve to cap some of the hydroxyl groups of the prepolymer preventing them from undergoing silylation. Amounts of such hydroxyl-reactive monomeric reactants and isocyanatosilanes that can be utilized for partial silylation herein can be readily determined for a specific hydroxyl-terminated polyuretehane prepolymer employing routine experimental testing.
- Pressure sensitive adhesive compositions of superior solvent-resistance can be obtained with the partially silylated polyurethanes described above. In addition to the partially silylated polyurethanes, a solvent-resistant pressure sensitive adhesive composition in accordance with the invention will typically include one or more additives such as fillers, tackifiers, silane adhesion promoters, plasticizers, solvents, thixotropic agents, U.V. stabilizers, antioxidants, cure catalysts, etc., in the usual amounts.
- Typical fillers suitable for addition to the pressure-sensitive adhesive compositions of this invention include fumed silica, precipitated silica and calcium carbonates. Treated calcium carbonates having particle sizes from about 0.07µ to about 4µ are particularly useful and are available under several trade names: Ultra Pflex, Super Pflex, Hi Pflex from Specialty in Minerals; Winnofil SPM, SPT from Zeneca Resins; Hubercarb lat, Hubercarb 3Qt and Hubercarb W from Huber and Kotomite from ECC. These fillers can be used either alone or in combination. The fillers can comprise up to about 200 parts per 100 parts of the silylated polymer component(s) with from about 80 to about 150 parts filler per 100 parts polymer being suitable for many adhesive applications.
- The pressure sensitive adhesive composition can contain from about 20 to about 60 parts, and advantageously from about 30 to about 50 parts, of one or more known of conventional tackifiers per 100 parts of silylated polyurethane polymer. Examples of suitable tackifiers are MQ silicone resins (for which a curing catalyst such as benzoyl peroxide will ordinarily be included), terpene oligomers, coumarone/indene resins, aliphatic, petrochemical resins, and modified phenolic resins.
- Silane adhesion promoters can be employed at levels of from about 0.5 to about 5 parts per hundred parts of the silylated polyurethane polymer with from about 0.8 to about 1.5 parts per hundred parts polymer being especially advantageous. Suitable adhesion promoters include Silquest A-1120 silane, Silquest A-2120 silane, Silquest A-1170 silane and Silquest A-187 silane, all of which are available from GE Silicones.
- Exemplary plasticizers include phthalates, dipropylene and diethylene glycol dibenzoates and mixtures thereof, epoxidized soybean oil, and the like. Dioctyl and diisodecylphthalate are commercially available under the trade names Jayflex DOP and JayFlex DIDP from Exxon Chemical. The dibenzoates are available as Benzoflex 9-88, Benzoflex 50 and Benzoflex 400 from Velsicol Chemical Corporation. Epoxidized soybean oil is available from Houghton Chemical Corporation as Flexol EPO. The plasticizer can comprise up to about 100 parts of the silylated polyurethane polymer with from about 40 to about 80 parts per hundred parts of silylated polymer being satisfactory in many cases.
- Useful solvents include aromatic, aliphatic and esters ranging in amounts of from about 25 to about 75 per hundred parts by weight of silylated polyurethane prepolymer.
- Illustrative of useful thixotropic agents are various castor waxes, fumed silica, treated clays and polyamides. These additives typically comprise about 1 to about 10 parts per hundred parts of silylated polyurethane prepolymer with from about 1 to about 6 parts being useful for most applications. The thixotropes include those available as: Aerosil from Degussa, Cabo-Sil TS 720 from Cabot, Castorwax from CasChem, Thixatrol and Thixcin from Rheox and Dislon from King Industries. If the thixotrope is reactive with silane (e.g., silica), adjustments to the amount formulated may be needed to compensate therefor.
- U. V. stabilizers and/or antioxidants can be incorporated into the pressure sensitive adhesive compositions of this invention in an amount of from 0 to about 5 parts per hundred parts silylated polyurethane polymer with from about 0.5 to about 2 parts providing generally good results. These materials are available from Ciba-Geigy under the trade names Tinuvin 770, Tinuvin 327, Tinuvin 213, Tinuvin 622 and Irganox 1010.
- Suitable cure catalysts are the same as those previously described for preparation of the silylated polyurethane polymers. The catalysts typically compromise from about 0.01 to about 3 parts per hundred parts polymer with from about 0.01 to about 1.0 parts per hundred parts of polymer being entirely suitable in many cases.
- After mixing, the pressure sensitive adhesive compositions are cured by exposure to moisture. Curing conditions typically include ambient temperature, e.g., about 23° C. and 50% relative humidity for 3 days and 37° C. and 95% relative humidity for another 4 days. Alternatively water can be dissolved in an appropriate solvent such as isopropanol followed by mixing with the adhesive composition and coated, cured in convensional adhesive cure ovens known in the art.
- The following examples are illustrative of the silylated polymers of this invention and solvent-resistant pressure sensitive adhesive compositions containing same.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 250.0 g of hydroxyl-terminated polybutadiene Poly bd® R-20LM resin (SpecialChem) possessing a hydroxyl number of 101. This resin was dried using a nitrogen purge at 85 °C over night. The resin was cooled to 65 °C followed by addition of 0.21 g of a 10 wt% solution of dibutyltin dilaurate and agitation for 30 minutes. Next, 75.2 g of isophorone diisocyanate (IPDI) was added drop wise over a two-minute period with agitation. An exotherm to 88 °C was observed and the temperature was reduced to, and held at, 72-75 °C for 45 minutes. The wt% NCO was determined by standard methodology and found to be 2.74 wt%. At this point, 49.7g of N-ethylamino isobutyltrimethoxysilane was added and agitation continued at temperature for 1 hour followed by cooling to room temperature. An approximately 15 g sample of the reaction product was dissolved in 35 g of toluene containing 0.37 g benzoyl peroxide. This mixture was bar-coated onto a 2 mil polyester film to yield a 1 mil dry adhesive thickness, then cured for 5minutes at 150 °C. Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto a smooth surface Delrin® (DuPont's polyoxymethylene) plaque with a 100 g weight. The lap shear samples were suspended in xylene that was slowly stirred using a magnetic stirrer and bar. Testing was conducted in duplicate and times to adhesive failure were 200 and 165 minutes.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 120.0 g of hydroxyl-terminated polybutadiene Poly bd® R-45M (SpecialChem) resin possessing a hydroxyl number of 40.4 and 120.0 g of a polypropylene polyol Acclaim® 4200 (SpecialChem) possessing a hydroxyl number of 28. The polyols were dried to reduce their moisture level. To this mixture was added 24.5 g of isophorone diisocyanate followed by heating for 2 hours at approximately 80 °C which was then decreased to 70-75 °C for 3 hours at which point 0.2g of a 10 wt% solution of dibutyltin dilaurate was added and the temperature maintained for 1 hour. The wt% NCO was determined to be 0.8 wt%. At this point, 24.5g of N-ethylaminoisobutyltrimethoxysilane was added and agitation continued while cooling to room temperature. A sample was coated and cured as in Example 1 except curing was conducted for 2 minutes at 177 °C. Testing was carried out as in Example 1. Time to adhesive failure was found to be greater than 200 minutes.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 200.0 g hydroxyl-terminated polybutadiene Krasol® LBHP2000 (Sartomer) resin possessing a hydroxyl number of 46 and 200.0 g toluene which was then refluxed to reduce moisture level. To this was added 35.9 g of isophorone diisocyanate after cooling to 85 °C. Temperature was maintained at 85-95 °C for 3 hours at which point 0.1 g of a 10 wt% solution of dibutyltin dilaurate was added and continued at temperature for 1 hour. The wt% NCO was determined to be 2.4 wt%. At this point, 32.4 g of N-ethylaminoisobutyltrimethoxysilane was added and agitation continued while cooling to room temperature. A sample was coated and cured as in Example 1 except curing was conducted for 3 minutes at 150 °C. Testing was carried out as in Example 1. The wt% benzoyl peroxide based on solids was 1.5 wt%. Time to adhesive failure on a smooth surface Delrin® plaque was 200 and 316 minutes and on glass slides greater then 24 hours at which point testing was terminated. Time to adhesive failure for the sample dried as above without peroxide catalyst was 30 minutes on Delran and 35 minutes on glass.
- This reaction product was blended 1:1 on a weight basis with Norsolene A-110 (SpecialChem) resin then cured using 1 wt% benzoyl peroxide for 5 minutes at 130° C. Time to failure was 210 minutes for the Delrin® substrate.
- To 15 g of the above sample was added a hydrogen polysiloxane containing 0.72 wt% hydrogen, 0.05 g of a 1 wt% platinum catalyst and 10 g toluene. This mixture was coated and cured at 135 °C for 10 minutes. Time to adhesive failure on a smooth surface Delran plaque was found to be 83 and 85 minutes and on glass slides was 50 and 50 minutes.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 100.0 g hydroxyl-terminated polybutadiene Krasol® HLBHP3000 (Sartomer) resin possessing a hydroxyl number of 31 and 85.0 g polycaprolactone polyol Capa® 2302A possessing a hydroxyl number of 38 followed by heating at 100-110 °C to reduce moisture level. To this mixture was added 8.4 g of isophorone diisocyanate after cooling to 80 °C. The temperature was maintained at 80-95°C for 3 hours at which point 0.4 g of a 10 wt% solution of 2,2'-dimorpholinediethyl-ether was added and continued at temperature for 3 hours. The temperature was reduced to 65 °C and 8.0 g 3-isocyanatopropyltrimethoxysilane was added and further heated at 70-80 °C for 4 hours. A sample was coated and cured as in Example 1 and time to adhesive failure on a smooth surface Delrin® plaque was found to be 70 and 75 minutes and on glass slides 40 and 60 minutes.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 100.0 g a,a,a-trifluorotoluene, 100.0 g hydroxyl-terminated polybutadiene Poly bd® LF3 resin possessing a hydroxyl number of 49.4 and 37.0 g HOCH2 CH2(CF2)∼10 CF3Zonyl® BA-LD (DuPont) possessing a hydroxyl number of 92 which was then heated to reduce moisture level. To this mixture was added 27.7 g of isophorone diisocyanate followed by the addition of 0.1 g of a 10 wt% solution of dibutyltin dilaurate with the temperature being maintained at 65-75 °C for 3 hours. The wt% NCO was determined to be 1.3 wt%. At this point, 17.6 g of N-ethylaminoisobutyltrimethoxysilane was added and agitation continued while cooling to room temperature. A sample was coated and cured as in Example 1 and time to adhesive failure on a smooth surface Delrin® plaque was found to be 30 minutes and on glass slides 145 minutes.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 100.0 g a,a,a-trifluorotoluene, 100.0 g hydroxyl-terminated polybutadiene Poly bd® R45HTLO (SpecialChem) resin possessing a hydroxyl number of 45.4 and 18.4 g HOCH2 CH2(CF2)∼10 CF3Zonyl® BA-LD (DuPont) possessing a hydroxyl number of 92 followed by heating to reduce moisture level. To this mixture was added 22.0 g of isophorone diisocyanate followed by addition of 0.1 g of a 10 wt% solution of dibutyltin dilaurate, the temperature being maintained at 65-75 °C for 3 hours. The wt% NCO was determined to be 0.7 wt%. At this point, 13.3 g of N-ethylaminoisobutyltrimethoxysilane was added and agitation continued while cooling to room temperature. A sample was coated and cured as in Example 1 and time to adhesive failure on a smooth surface Delrin® plaque was found to be 250 minutes and on glass slides 400 minutes.
- These examples illustrate silylated polymers prepared from hydroxyl-terminated polybutadienes of different number average molecular weights, blends of hydroxyl-terminated polybutadienes, various NCO/OH ratios for preparing the polyurethane prepolymers and pressure sensitive adhesive compositions containing the silylated polymers and optional tackifier.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 100.0 g of hydroxyl-terminated polybutadiene resin possessing a hydroxyl number as noted in Table 1, 100.0 g of toluene. The reaction mixture was dried by refluxing for 1 hour under a nitrogen atmosphere followed by cooling to below 50 °C then 0.05 g of a 10wt% solution of dibutyltin dilaurate was added and agitated for 30 minutes. Next, isophorone diisocyanate (IPDI) was added to achieve the NCO/OH ratio as noted in Table 1 below with continued agitation. The reactants were heated at 60-70 °C for 1 hour. A sample was taken for wt% NCO which was determined by standard methodology, the results being set forth in Table 1. To the reaction mixture was added N-ethylaminoisobutyltrimethoxysilane, the amount as noted in Table 1, and agitation continued at temperature for 30-60 minutes with cooling to room temperature. Solids were adjusted to 50.0 wt%. A sample of an approximately 15 g sample of the reaction product was dissolved in 3.8 g toluene having 0.15 g benzoyl peroxide dissolved therein. All samples were bar-coated onto a 2 mil polyester film to yield an approximate 1 mil dry adhesive thickness, air-dried 10 minutes then cured for 5 minutes at 150 °C. Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto 1 minute preheated at 135 °C to a smooth surface Delrin® plaque and a glass slide with a 100 g weight attached to the opposite end. The lap shear samples were suspended in xylene that was slowly stirred using a magnetic stirrer and bar. Times to adhesive failure are set forth in Table 1 below.
Table 1 Lap Shear Time, hrs Example OH-Terminated Polybutadiene g IPDI NCO/OH Ratio wt% NCO at Capping Smooth Delrin Glass 7 Poly bd R20LM 29.6 1.85 2.33 > 24 4.5 8 Poly bd R20LM 21.6 1.35 1.05 >71 0 9 Krasol LBH-P 2000 18.0 1.85 1.47 2 2.3 10 Krasol LBH-P 2000 13.1 1.35 0.59 3.25 4 11 Krasol LBH-P 2000/5000 @ 48/52 ratio 13.0 1.85 1.04 >24 >7.5 12 Krasol LBH-P 2000/5000 blend @ 48/52 ratio 9.5 1.35 0.45 >5.5 5.1 13 Krasol LBH-P 3000 9.5 1.35 0.29 >24 0.3 14 Krasol LBH-P 5000 8.5 1.85 0.63 >8 >8 15 Krasol LBH-P 5000 6.2 1.35 0.42 >24 3.6 16 Krasol LBH-P 5000 5.0 1.10 0.04 >5 >5 17 Example 16 with 2.5 g Eastotac 100W tackifier resin (Eastman) 4.5 4.5 18 Example 16 with 2.5 g Sylvarez TR1085 styrenated terpene tackifier resin (Arizona Chemical) >8 >8 - These examples illustrate silylated polymers made with hydroxyl-terminated saturated polybutadienes and with various NCO/OH ratios. The procedure of Examples 7-18 were substantially repeated for these examples. The results are set forth in Table 2 below.
Table 2 Lap Shear Time, hrs Example OH Terminated Polybutadiene g IPDI NCO/OH Ratio wt% NCO at Capping Smooth Delrin Glass 19 Krasol HLBH-P 3000 24.5 3.70 2.52 7 >9 20 Krasol HLBH-P 3000 8.9 1.35 0.50 1.5 0.3 21 Poly bd EPOL 16.0 1.85 1.22 1.25 1 22 Poly bd EPOL 11.6 1.35 0.55 >8.5 >8.5 23 Poly(ethylene-co-1,2-butylene)diol 16.6 1.85 0.90 >24 >7 24 Poly(ethylene-co-1,2-butylene)diol 12.1 1.35 0.55 8.25 6.75 - To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 50.0 g of hydroxyl-terminated polybutadiene resin Krasol LBH-P 5000 possessing a hydroxyl number of 21.7, 50.0 g of hydroxyl-terminated polybutadiene resin Krasol HLBH-P 3000 possessing a hydroxyl number of 31.4, 25.0 g of toluene, and 75.0 g of ethyl acetate. The contents were dried by refluxing for 1 hour under a nitrogen atmosphere followed by cooling to below 40 °C then 0.03 g of a 10wt% solution of dibutyltin dilaurate was added and agitated for 15 minutes. Next 6.2 g of isophorone diisocyanate was added for a NCO/OH ratio of 1.10 with continued agitation. The reactants were heated at 70-75 °C until the wt% NCO was determined to be 0.11 wt%. The reaction was cooled to 40 °C then was added 0.4 g of N-ethylaminoisobutyltrimethoxysilane and 0.4 g of N-ethylbutylamine diluted in 3.0 g ethylacetate with agitation. Solids were 51.7 wt%. A sample of an approximately 15 g sample of the reaction product was dissolved in 3.8 g toluene having 0.04 g benzoyl peroxide dissolved, was coated. A second sample without benzoyl peroxide was also coated. All samples were bar-coated onto a 2 mil polyester film to yield an approximately 1 mil dry adhesive thickness, air-dried 10 minutes then cured for 5 minutes at 150 °C. Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto a textured surface Delrin cassette and a glass slide with a 10 g weight attached to the opposite end. Time to adhesive failure for the benzoyl peroxide cured adhesive coating was 40 minutes for the cassette and 2 hours for the glass slide. The sample without benzoyl peroxide resulted in adhesive failure in 2 hours for the cassette and 2.5 hours for the glass slide.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 100.0 g of hydroxyl-terminated polybutadiene resin noted in Table 3 along with the hydroxyl number, and 100.0 g of toluene. The contents were dried by refluxing for 1 hour under a nitrogen atmosphere followed by cooling to below 40 °C then the grams of isophorone diisocyanate to achieve a NCO/OH ratio of 0.67 was added with continued agitation. After 60 minutes agitation 0.05 g of a 10wt% solution of dibutyltin dilaurate was added and agitated for 15 minutes. The reactants were heated at 65-70 °C until the wt% NCO was determined to be 0.0 wt%. The grams noted in table 3 of gamma-isocyanatopropyltrimethoxysilane (Silquest A-Link 35) was added and reacted until 0.0 wt% NCO was determined. The reaction was cooled to 40 °C. An approximately 15 g sample of the reaction product was dissolved in 3.8 g toluene having 0.04 g benzoyl peroxide dissolved therein was used for coating. All samples were bar-coated onto a 2 mil polyester film to yield an approximate 1 mil dry adhesive thickness, air-dried 10 minutes then cured for 5 minutes at 150 °C. Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto a smooth surface Delrin® plaque and a glass slide with a 10 g weight attached to the opposite end. Times to adhesive failure are set forth in Table 3 below.
Table 3 Lap Shear Time, hrs Example Number OH Terminated Polybutadiene OH Number mg KOH g IPDI g Silquest A-Link 35 Smooth Delrin Glass 26 Krasol LBH-P 2000 46 6.5 6.1 >24 0 27 Krasol LBH-P 3000 33.4 4.7 4.50 >24 >9 28 Krasol LBH-P 5000 21.7 3.1 2.3 >24 >9 29 Poly bd LF3 49.4 6.7 6.3 >72 6.8 30 Poly bd R45HTLO 45.4 4.9 4.60 >24 >5.5 31 Poly bd R20LM 101 10.9 10.2 2.25 2.5 32 Poly bd EPOL 51.6 5.8 5.4 0.55 0.78 - The preparative procedures of Examples 26-32 were substantially repeated except that blends of polyols and an NCO/OH of 0.9 to achieve higher molecular weight polyurethane prepolymers were employed. The results are set forth in Table 4 below.
Table 4 Example Number OH Terminated Polybutadiene Ratios of Polyols g IPDI g Silquest A-Link 35 wt% Benzoyl Peroxide Textured Delrin Cassette, hrs Peel Adhesion, Stainless Steel 12"/min., 180° 33 Krasol LBH-P 2000/5000 1/1.08 6.3 1.3 0 3.5 1173 g/in 0.25 2.17 0.5 2.5 1561 g/in 34 Krasol LBH-P 2000/5000/R45 HTLO 1/1.08/2.0 8 6.4 1.4 0 0.25 0.25 2.5 194 g/in 35 Krasol LBH-P 5000 4.1 0.9 0 3.25 36 Krasol HLBH-P 3000 6.0 1.3 0 3.5 903 g/in 0.5 3.5 784 g/in 1 1.8 37 Krasol LBH-P 2000/5000/R45 HTLO 2/1/0.76 6.4 0.4 0 2.5 0.5 2.75 1295 g/in 38 Krasol LBH-P 2000/5000/R45 HTLO 1/2/0.76 6.4 0.5 0.5 3.5 2270 g/in - This example illustrates hydrosilylation crosslinking of silylated polyurethane polymer.
- To a reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 96.0 g of hydroxyl-terminated polybutadiene resin Krasol LBH-P 2000, 104.0 g of hydroxyl-terminated polybutadiene resin Krasol LBH-P 5000 and 100.0 g of ethylacetate. The contents were dried by refluxing for 1 hour under a nitrogen atmosphere followed by cooling to below 40 °C then 0.05 g of a 10wt% solution of dibutyltin dilaurate was added with continued agitation. After 15 minutes 12.7 g of isophorone diisocyanate was added. The reactants were heated at 70-75 °C until the wt% NCO was determined to be 0.0 wt%. Next, 2.7 g of λ-isocyanatopropyltrimethoxysilane was added and reacted until 0.0 wt% NCO was measured. The reaction mixture was cooled to 40 °C. A sample of approximately 15 g of the reaction product dissolved in 3.8 g toluene, 0.03 g M'0.9M0.1D2.8DH 7.2T0.1M0.1 silicone resin wherein M' is a dimethylstyrylsiloxy group, 25 ppm rhodium provided as an ethanol solution of tris(dibutylsulfide)rhodium(III)trichloride containing 1.4 wt% rhodium, was used for coating. The coated sample was bar-coated onto a 2 mil polyester film to yield an approximate 1 mil dry adhesive thickness, air-dried 10 minutes then cured for 5 minutes at 150 °C. Lap shear samples were prepared with 0.25 inch x 1.0 inch overlap onto a textured surface Delrin® cassette with a 10 g weight attached to the opposite end. Time to adhesive failure was 3.5 hours.
- This example illustrates the silylation of an hydroxyl terminated polyurethane prepolymer with an isocyanato silane capping agent.
- To a resin reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 72.5 g of hydroxyl terminated polybutadiene Krasol LBH-P 2000 resin containing a hydroxyl number of 46, 145.0 g of hydroxyl terminated polybutadiene Krasol LBH-P 5000 resin containing a hydroxyl number of 21.7, 32.5 g of hydroxyl terminated polybutadiene Poly-bd R20LM resin containing a hydroxyl number of 101 and 400.3 g of ethyl acetate. Refluxed for 2 hours to dry the mixture followed by cooling to 75-80 °C. To this was added 0.27 g of a 10 wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane with agitation for 15 minutes. Next 18.6 g of isophorone diisocyanate was added for an NCO/OH equivalent ratio of 0.95. The reactants were heated at 75-80 °C until the wt% NCO was determined per standard methodology and found to be 0.0 wt% followed by drop wise addition of 1.34 g isocyanatopropyltrimethoxysilane. Heating was continued until wt% NCO was 0.0 wt% then the composition was cooled to room temperature. A 25 g sample was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness. The adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C. Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved. Shear adhesion failure temperature (SAFT) for 1.0 inch x 1.0 inch overlap and 1 Kg weight was determined to be 275 °C.
- This comparative example is similar to Example 40 except that the polyurethane prepolymer was not silylated.
- To a resin reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 72.5 g of hydroxyl terminated polybutadiene Krasol- LBH-P 2000 resin containing a hydroxyl number of 46, 145.0 g of hydroxyl terminated polybutadiene Krasol LBH-P 5000 resin containing a hydroxyl number of 21.7, 32.5 g of hydroxyl terminated polybutadiene Poly-bd R20LM resin containing a hydroxyl number of 101 and 400.3 g of ethyl acetate. Refluxed for 2 hours to dry the mixture followed by cooling to 75-80 °C. To this was added 0.27 g of a 10 wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane with agitation for 15 minutes. Next 18.6 g of isophorone diisocyanate was added for an NCO/OH equivalent ratio of 0.95. The reactants were heated at 75-80 °C until the wt% NCO was determined per standard methodology and found to be 0.0 wt% followed by cooling to room temperature. A 25 g sample was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness. The adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C. Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved. Shear adhesion failure temperature (SAFT) for 1.0 inch x 1.0 inch overlap and 1 Kg weight was determined to be 59 °C.
- To a resin reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 58.0 g of hydroxyl terminated polybutadiene Krasol- LBH-P 2000 resin containing a hydroxyl number of 46, 116.0 g of hydroxyl terminated polybutadiene Krasol LBH-P 5000 resin containing a hydroxyl number of 21.7, 26.0 g of hydroxyl terminated polybutadiene Poly bd R20LM resin containing a hydroxyl number of 101 and 333.2 g of ethyl acetate. Refluxed for 2 hours to dry the mixture followed by cooling to 75-80 °C. To this was added 1.77 g of a 1 wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane with agitation for 15 minutes. Next 16.6 g of isophorone diisocyanate was added for an NCO/OH equivalent ratio of 1.06. The reactants were heated at 75-80 °C until the wt% NCO was determined per standard methodology and found to be 0.06 wt% followed by cooling to room temperature. A solution of 20 g ethyl acetate and 1.7 g N-ethylaminoisobutyltrimethoxysilane was added drop wise. A 25 g sample of this composition was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness. The adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C. Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved. Shear adhesion failure temperature (SAFT) for 1.0 inch x 1.0 inch overlap and 1 Kg weight was determined to be greater than 281°C.
- This comparative example is similar to Example 42 except that the polyurethane prepolymer was not silylated.
- To a resin reaction vessel equipped with mixing capability, condenser, nitrogen atmosphere and heating was added 58.0 g of hydroxyl terminated polybutadiene Krasol LBH-P 2000 resin containing a hydroxyl number of 46, 116.0 g of hydroxyl terminated polybutadiene Krasol LBH-P 5000 resin containing a hydroxyl number of 21.7, 26.0 g of hydroxyl terminated polybutadiene Poly bd R20LM resin containing a hydroxyl number of 101 and 333.2 g of ethyl acetate. Refluxed for 2 hours to dry the mixture followed by cooling to 75-80 °C. To this was added 1.77 g of a 1 wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane with agitation for 15 minutes. Next 16.6 g of isophorone diisocyanate was added for an NCO/OH equivalent ratio of 1.06. The reactants were heated at 75-80 °C until the wt% NCO was determined per standard methodology and found to be 0.03 wt% followed by cooling to room temperature. Drop wise 0.4 g ethylbutyl amine and 20 g ethyl acetate solution was added to the prepolymer to yield an organic amine terminated polyurethane. A 25 g sample was dissolved in 12 g ethyl acetate, 0.2 g of a 1 wt% 1.0 g of a 1wt% toluene solution of dimethylbis[(1-oxoneodecyl)oxy]stannane was bar coated onto 2 mil polyester film to yield an approximate 0.4 mil dry adhesive thickness. The adhesive was air dried 10 minutes, followed by 10 minutes at 80 °C. Lap shear samples were prepared with 1.0 inch x 1.0 inch overlap onto a glass slide with a 10 g weight attached to the opposite end. Time to failure was >7 hours and adhesive dissolved. Shear adhesion failure temperature (SAFT) for 1.0 inch x 1.0 inch overlap and 1 Kg weight was determined to be 62 °C.
- While the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out the process of the invention but that the invention will include all embodiments falling within the scope of the appended claims.
- As can be seen from the above, the present invention generally relates to the following aspects:
- 1. A silylated polymer obtained by the process which comprises:
- a) reacting hydroxyl-terminated polybutadiene and, optionally, chain extender and/or other polyol, with polyisocyanate to provide isocyanate-terminated polyurethane prepolymer; and,
- b) reacting the isocyanate-terminated polyurethane prepolymer with silane possessing hydrolyzable functionality and isocyanate-reactive functionality to provide silylated polyurethane prepolymer wherein less than all of the isocyanate groups of the isocyanate-terminated polyurethane prepolymer are silylated; and,
- c)carrying out step (b) in the additional presence of monofunctional isocyanate-capping reactant to cap non-silylated isocyanate groups in the silylated polyurethane.
- 2. The silylated polymer of aforementioned Aspect 1 wherein the silane is a primary or secondary aminosilane of the general formula:
X-R1-Si(R2)x(OR3)3-x.
wherein X is -SH or -NHR4 in which R4 is H, a monovalent hydrocarbon group of up to 8 carbon atoms or -R5-Si(R6)y(OR7)3-y, R1 and R5 each is the same or different divalent hydrocarbon group of up to 12 carbon atoms, optionally containing one or more heteroatoms, each R2 and R6 is the same or different monovalent hydrocarbon group of up to 8 carbon atoms, each R3 and R7 is the same or different alkyl group of up to 6 carbon atoms and x and y each, independently, is 0, 1 or 2. - 3. The silylated polymer of aforementioned Aspect 2 wherein the silane is a secondary aminosilane.
- 4. The silylated polymer of aforementioned Aspect 2 wherein the silane is a mercaptosilane.
- 5. The silylated polymer of aforementioned Aspect 2 wherein the silane is selected from the group consisting of 2-mercaptoethyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 2-mercaptopropyl triethoxysilane, 3 -mercaptopropyl triethoxysilane, 2-mercaptoethyl tripropoxysilane, 2-mercaptoethyl tri sec-butoxysilane, 3-mercaptopropyl tri-t-butoxysilane, 3-mercaptopropyl triisopropoxysilane, 3-mercaptopropyl trioctoxysilane, 2-mercaptoethyl tri-2'-ethylhexoxysilane, 2-mercaptoethyl dimethoxy ethoxysilane, 3-mercaptopropyl methoxyethoxypropoxysilane, 3-mercaptopropyl dimethoxy methylsilane, 3-mercaptopropyl methoxy dimethylsilane, 3-mercaptopropyl ethoxy dimethylsilane, 3-mercaptopropyl diethoxy methylsilane, 3-mercaptopropyl cyclohexoxy dimethyl silane, 4-mercaptobutyl trimethoxysilane, 3-mercapto-3-methylpropyltrimethoxysilane, 3-mercapto-3-methylpropyl-tripropoxysilane, 3-mercapto-3-ethylpropyl-dimethoxy methylsilane, 3-mercapto-2-methylpropyl trimethoxysilane, 3-mercapto-2-methylpropyl dimethoxy phenylsilane, 3-mercaptocyclohexyl-trimethoxysilane, 12-mercaptododecyl trimethoxy silane, 12-mercaptododecyl triethoxy silane, 18-mercaptooctadecyl trimethoxysilane, 18-mercaptooctadecyl methoxydimethylsilane, 2-mercapto-2-methylethyl-tripropoxysilane, 2-mercapto-2-methylethyl-trioctoxysilane, 2-mercaptophenyl trimethoxysilane, 2-mercaptophenyl triethoxysilane, 2-mercaptotolyl trimethoxysilane, 2-mercaptotolyl triethoxysilane, 1-mercaptomethyltolyl trimethoxysilane, 1-mercaptomethyltolyl triethoxysilane, 2-mercaptoethylphenyl trimethoxysilane, 2-mercaptoethyiphenyl triethoxysilane, 2-mercaptoethyltolyl trimethoxysilane, 2-mercaptoethyltolyl triethoxysilane, 3-mercaptopropylphenyl trimethoxysilane, 3-mercaptopropylphenyl triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxy-silane, N-methyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino-2-methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropyl-methyldimethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, 3-(N-methyl-2-amino-1-methyl-1-ethoxy)-propyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethyl-butyldimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyltrimethoxy-silane, N-(cyclohexyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy-silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, bis-(3-trimethoxysilyl-2-methylpropyl)amine and N-(3'-trimethoxysilylpropyl)-3-amino-2-methylpropyltri-methoxysilane.
- 6. The silylated polyurethane of aforementioned Aspect 2 wherein not more than about 95 percent of the isocyanate groups of the isocyanate-terminated polyurethane prepolymer are silylated.
- 7. A silylated polymer obtained by the process which comprises:
- a) reacting hydroxyl-terminated polybutadiene and, optionally, chain extender and/or other polyol, with polyisocyanate to provide hydroxyl-terminated polyurethane prepolymer; and,
- b) reacting the hydroxyl-terminated polyurethane prepolymer with isocyanatosilane possessing hydrolyzable functionality to provide silylated polyurethane.
- 8. The silylated polyurethane of aforementioned Aspect 7 wherein in step (b) not more than about 95 percent of the hydroxyl groups of the hydroxyl-terminated polyurethane prepolymer are silylated.
- 9. The silylated polyurethane of aforementioned Aspect 7 wherein in step (b) less than all of the hydroxyl groups of the hydroxyl-terminated polyurethane prepolymer are silylated and, optionally, step (b) is carried out in the additional presence of monofunctional hydroxyl-capping reactant to cap non-silylated hydroxyl groups in the silylated polyurethane.
- 10. The silylated polyurethane of aforementioned Aspect 9 wherein in step (b) not more than about 95 percent of the hydroxyl groups of the hydroxyl-terminated polyurethane prepolymer are silylated.
- 11. A curable pressure sensitive adhesive composition comprising a pressure sensitive adhesive amount of at least one partially silylated polyurethane of aforementioned Aspect 1.
- 12. A curable pressure sensitive adhesive composition comprising a pressure sensitive adhesive amount of at least one partially silylated polyurethane of aforementioned Aspect 9.
- 13. The curable pressure sensitive adhesive composition of aforementioned Aspect 11 comprising at least one additional component selected from the group consisting of filler, tackifier, silane adhesion promoter, plasticizer, solvent, thixotropic agent, U.V. stabilizer, antioxidant and curing catalyst.
- 14. The curable pressure sensitive adhesive composition of aforementioned Aspect 11 comprising a tackifying amount of MQ tackifier resin and a curing catalyst therefor.
- 15. The cured pressure sensitive adhesive composition of aforementioned Aspect 11.
- 16. The cured pressure sensitive adhesive composition of aforementioned Aspect 14.
- 17. The curable pressure sensitive adhesive composition of aforementioned Aspect 12 comprising at least one additional component selected from the group consisting of filler, tackifier, silane adhesion promoter, plasticizer, solvent, thixotropic agent, U.V. stabilizer, antioxidant and curing catalyst.
- 18. The curable pressure sensitive adhesive composition of aforementioned Aspect 12 comprising a tackifying amount of MQ tackifier resin and a curing catalyst therefor.
- 19. The cured pressure sensitive adhesive composition of aforementioned Aspect 12.
- 20. The cured pressure sensitive adhesive composition of aforementioned Aspect 18.
- 21. The cured pressure sensitive adhesive composition of aforementioned Aspect 13.
- 22. The cured pressure sensitive adhesive composition of aforementioned Aspect 17.
Claims (10)
- A silylated polymer obtained by the process which comprises:a) reacting hydroxyl-terminated polybutadiene and, optionally, chain extender and/or other polyol, with polyisocyanate to provide hydroxyl-terminated polyurethane prepolymer; and,b) reacting the hydroxyl-terminated polyurethane prepolymer with isocyanatosilane possessing hydrolyzable functionality to provide silylated polyurethane.
- The silylated polyurethane of Claim 1 wherein in step (b) not more than about 95 percent of the hydroxyl groups of the hydroxyl-terminated polyurethane prepolymer are silylated.
- The silylated polyurethane of Claim 1 wherein in step (b) less than all of the hydroxyl groups of the hydroxyl-terminated polyurethane prepolymer are silylated and, optionally, step (b) is carried out in the additional presence of monofunctional hydroxyl-capping reactant to cap non-silylated hydroxyl groups in the silylated polyurethane.
- The silylated polyurethane of Claim 3 wherein in step (b) not more than about 95 percent of the hydroxyl groups of the hydroxyl-terminated polyurethane prepolymer are silylated.
- A curable pressure sensitive adhesive composition comprising a pressure sensitive adhesive amount of at least one partially silylated polyurethane of Claim 3.
- The curable pressure sensitive adhesive composition of Claim 5 comprising at least one additional component selected from the group consisting of filler, tackifier, silane adhesion promoter, plasticizer, solvent, thixotropic agent, U.V. stabilizer, antioxidant and curing catalyst.
- The curable pressure sensitive adhesive composition of Claim 5 comprising a tackifying amount of MQ tackifier resin and a curing catalyst therefor.
- The cured pressure sensitive adhesive composition of Claim 5.
- The cured pressure sensitive adhesive composition of Claim 6.
- The cured pressure sensitive adhesive composition of Claim 7.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/119,263 US20060247369A1 (en) | 2005-04-29 | 2005-04-29 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
US11/297,757 US7405259B2 (en) | 2005-04-29 | 2005-12-08 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
EP06749953.3A EP1874840B1 (en) | 2005-04-29 | 2006-04-12 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
PCT/US2006/013752 WO2006118766A1 (en) | 2005-04-29 | 2006-04-12 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06749953.3A Division-Into EP1874840B1 (en) | 2005-04-29 | 2006-04-12 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
EP06749953.3A Division EP1874840B1 (en) | 2005-04-29 | 2006-04-12 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3666808A1 true EP3666808A1 (en) | 2020-06-17 |
EP3666808B1 EP3666808B1 (en) | 2021-06-23 |
Family
ID=36741177
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06749953.3A Active EP1874840B1 (en) | 2005-04-29 | 2006-04-12 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
EP20153362.7A Active EP3666808B1 (en) | 2005-04-29 | 2006-04-12 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06749953.3A Active EP1874840B1 (en) | 2005-04-29 | 2006-04-12 | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
Country Status (10)
Country | Link |
---|---|
US (1) | US7405259B2 (en) |
EP (2) | EP1874840B1 (en) |
JP (1) | JP4988709B2 (en) |
KR (1) | KR101359995B1 (en) |
AU (1) | AU2006242705B2 (en) |
BR (1) | BRPI0608331A2 (en) |
CA (1) | CA2605264A1 (en) |
NO (1) | NO20075580L (en) |
RU (1) | RU2007144208A (en) |
WO (1) | WO2006118766A1 (en) |
Families Citing this family (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003300293B8 (en) * | 2002-12-20 | 2010-01-14 | Chemocentryx, Inc. | Inhibitors of the binding of chemokines I-TAC or SDF-1 to the CCXCKR2 receptor |
DE102005003632A1 (en) | 2005-01-20 | 2006-08-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Catheter for the transvascular implantation of heart valve prostheses |
US7956123B2 (en) * | 2005-10-24 | 2011-06-07 | Momentive Performance Materials Inc. | Solvent resistant polyurethane adhesive compositions |
DE102005051849B4 (en) | 2005-10-28 | 2010-01-21 | JenaValve Technology Inc., Wilmington | Device for implantation and attachment of heart valve prostheses |
US8247514B2 (en) * | 2006-09-01 | 2012-08-21 | Momentive Performance Materials Inc. | Silylated polyurethane compositions and adhesives therefrom |
US8247079B2 (en) * | 2006-09-01 | 2012-08-21 | Momentive Performance Materials Inc. | Laminate containing a silylated polyurethane adhesive composition |
US7976951B2 (en) | 2006-11-14 | 2011-07-12 | Momentive Performance Materials Inc. | Laminate containing an adhesive-forming composition |
US7829116B2 (en) * | 2006-11-14 | 2010-11-09 | Momentive Performance Materials Inc. | Adhesive-forming composition and blend of adhesives obtained therefrom |
DE102006054289A1 (en) * | 2006-11-17 | 2008-05-21 | Bayer Materialscience Ag | Nanoparticle-modified polyisocyanates |
US7896915B2 (en) | 2007-04-13 | 2011-03-01 | Jenavalve Technology, Inc. | Medical device for treating a heart valve insufficiency |
US9138315B2 (en) | 2007-04-13 | 2015-09-22 | Jenavalve Technology Gmbh | Medical device for treating a heart valve insufficiency or stenosis |
ES2903231T3 (en) | 2008-02-26 | 2022-03-31 | Jenavalve Tech Inc | Stent for positioning and anchoring a valve prosthesis at an implantation site in a patient's heart |
US8317858B2 (en) | 2008-02-26 | 2012-11-27 | Jenavalve Technology, Inc. | Stent for the positioning and anchoring of a valvular prosthesis in an implantation site in the heart of a patient |
US9168130B2 (en) | 2008-02-26 | 2015-10-27 | Jenavalve Technology Gmbh | Stent for the positioning and anchoring of a valvular prosthesis in an implantation site in the heart of a patient |
US8398704B2 (en) | 2008-02-26 | 2013-03-19 | Jenavalve Technology, Inc. | Stent for the positioning and anchoring of a valvular prosthesis in an implantation site in the heart of a patient |
US8465540B2 (en) | 2008-02-26 | 2013-06-18 | Jenavalve Technology, Inc. | Stent for the positioning and anchoring of a valvular prosthesis |
US9044318B2 (en) | 2008-02-26 | 2015-06-02 | Jenavalve Technology Gmbh | Stent for the positioning and anchoring of a valvular prosthesis |
JP5561166B2 (en) | 2008-09-05 | 2014-07-30 | 旭硝子株式会社 | Adhesive body, adhesive sheet and use thereof |
KR101308253B1 (en) * | 2008-10-08 | 2013-09-13 | 아사히 가라스 가부시키가이샤 | Adhesive laminate |
DE102009011163A1 (en) | 2008-12-16 | 2010-07-08 | Tesa Se | Adhesive tape, in particular for bonding photovoltaic modules |
US8138297B2 (en) | 2009-02-09 | 2012-03-20 | Momentive Performance Materials Inc. | Moisture-curable silylated polymer possessing improved storage stability |
DE102009011167A1 (en) | 2009-03-04 | 2010-09-09 | Tesa Se | PSA |
US11278406B2 (en) | 2010-05-20 | 2022-03-22 | Jenavalve Technology, Inc. | Catheter system for introducing an expandable heart valve stent into the body of a patient, insertion system with a catheter system and medical device for treatment of a heart valve defect |
US10856978B2 (en) | 2010-05-20 | 2020-12-08 | Jenavalve Technology, Inc. | Catheter system |
JP2013526388A (en) | 2010-05-25 | 2013-06-24 | イエナバルブ テクノロジー インク | Artificial heart valve, and transcatheter delivery prosthesis comprising an artificial heart valve and a stent |
DE102011001303A1 (en) * | 2011-03-16 | 2012-09-20 | Continental Reifen Deutschland Gmbh | rubber compound |
DE102011088170A1 (en) | 2011-12-09 | 2013-06-13 | Bayer Materialscience Aktiengesellschaft | Reactive pressure-sensitive adhesives |
FR2985215B1 (en) | 2011-12-28 | 2014-09-19 | Saint Gobain Performance Plast | POLYMERIC COATINGS DEPOSITED ON SUBSTRATES BY THERMAL PROJECTION TECHNIQUES |
CN103182808A (en) | 2011-12-28 | 2013-07-03 | 圣戈班高功能塑料集团 | Multilayer complex comprising fluorine-containing polymer surface layer and non-fluorinated polymer transition layer |
KR101400732B1 (en) * | 2012-04-16 | 2014-05-30 | 금호타이어 주식회사 | Tire rubber composition improved property of rolling resistance and wear resistance |
TWI486367B (en) | 2012-05-30 | 2015-06-01 | Nippon Soda Co | Polyurethane |
US20140010484A1 (en) | 2012-06-29 | 2014-01-09 | Olaf Schmitjes | Slide bearing comprising a primer system as adhesion promoter |
US9803690B2 (en) | 2012-09-28 | 2017-10-31 | Saint-Gobain Performance Plastics Pampus Gmbh | Maintenance-free slide bearing with a combined adhesive sliding layer |
KR101310868B1 (en) * | 2013-02-26 | 2013-10-14 | 금호석유화학 주식회사 | End-modified diene polymer with alkoxysillane derivatives |
US9156981B2 (en) | 2013-07-24 | 2015-10-13 | Momentive Performance Materials Inc. | Moisture curable compositions with enhanced elongation and tear strength properties |
JP6563394B2 (en) | 2013-08-30 | 2019-08-21 | イェーナヴァルヴ テクノロジー インコーポレイテッド | Radially foldable frame for an artificial valve and method for manufacturing the frame |
US9321878B2 (en) | 2013-12-16 | 2016-04-26 | Momentive Performance Materials Inc. | Process for the preparation of silylated polyurethane polymers using titanium-containing and zirconium-containing catalysts |
CN107530168B (en) | 2015-05-01 | 2020-06-09 | 耶拿阀门科技股份有限公司 | Device and method with reduced pacemaker ratio in heart valve replacement |
CN107849218B (en) * | 2015-07-30 | 2021-03-05 | Sika技术股份公司 | Hydrophobic and highly elastic two-component polyurethane compositions with temperature-independent mechanical properties and adhesion |
EP3454795B1 (en) | 2016-05-13 | 2023-01-11 | JenaValve Technology, Inc. | Heart valve prosthesis delivery system for delivery of heart valve prosthesis with introducer sheath and loading system |
JP7094965B2 (en) | 2017-01-27 | 2022-07-04 | イエナバルブ テクノロジー インク | Heart valve imitation |
US11312816B2 (en) | 2017-04-12 | 2022-04-26 | Basf Se | Thermoplastic polyurethane and composite article |
WO2020026731A1 (en) * | 2018-08-03 | 2020-02-06 | 信越化学工業株式会社 | Room-temperature-curable polybutadiene resin composition, method for producing same, and packaged circuit board |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4118536A (en) * | 1976-10-08 | 1978-10-03 | Minnesota Mining And Manufacturing Company | Silane-terminated polycarbodiimide primers and composite coatings therefrom |
JPS5682863U (en) | 1979-11-30 | 1981-07-04 | ||
JPS57207663A (en) | 1981-06-15 | 1982-12-20 | Kongo Furotsukingu Kk | Hot-melt adhesive composition |
JPS59172575A (en) | 1983-03-23 | 1984-09-29 | Kao Corp | Hot-melt adhesive and its preparation |
JPS59174672A (en) | 1983-03-23 | 1984-10-03 | Kao Corp | Hot-melt adhesive |
JPS61218673A (en) | 1985-03-25 | 1986-09-29 | Agency Of Ind Science & Technol | Hot-melt adhesive curable with ionizing radiation |
JPS61218672A (en) | 1985-03-25 | 1986-09-29 | Agency Of Ind Science & Technol | Hot-melt adhesive curable with ionizing radiation |
JPS61218631A (en) | 1985-03-25 | 1986-09-29 | Agency Of Ind Science & Technol | Crosslinkable hot-melt adhesive |
JPS6147774B2 (en) | 1978-06-28 | 1986-10-21 | Ube Industries | |
JPS6289782A (en) | 1985-06-07 | 1987-04-24 | Asahi Glass Co Ltd | Hot-melt adhesive |
JPS6257480B2 (en) | 1978-10-07 | 1987-12-01 | Yunibaasaru Kongeitetsudo Botsukusu Mashiinari Hoorudeingu Ag | |
JPS6257479B2 (en) | 1981-03-31 | 1987-12-01 | Fuji Oil Co Ltd | |
JPS6257478B2 (en) | 1980-05-08 | 1987-12-01 | Tokura Kk | |
JPH03259981A (en) | 1990-03-12 | 1991-11-20 | Kuraray Co Ltd | Hot-melt adhesive composition |
JPH09165565A (en) | 1995-12-14 | 1997-06-24 | Kuraray Co Ltd | Adhesive composition |
US20020082333A1 (en) * | 2000-09-13 | 2002-06-27 | Rudiger Herpich | Silica gel-containing rubber compounds with organosilicon compounds as compounding agent |
US6641922B2 (en) * | 2001-01-17 | 2003-11-04 | A. Andrew Shores | Silicone and ionically modified isocyanate adduct |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5682863A (en) | 1979-12-12 | 1981-07-06 | Furukawa Electric Co Ltd:The | Hot-melt type adhesive composition |
US4345053A (en) * | 1981-07-17 | 1982-08-17 | Essex Chemical Corp. | Silicon-terminated polyurethane polymer |
JPS6257480A (en) | 1985-09-05 | 1987-03-13 | Agency Of Ind Science & Technol | Hot-melt adhesive curable with ionizing radiation |
JPS6257479A (en) | 1985-09-05 | 1987-03-13 | Agency Of Ind Science & Technol | Hot-melt adhesive for fiber and curable with ionizing radiation |
JPS6257478A (en) | 1985-09-05 | 1987-03-13 | Agency Of Ind Science & Technol | Hot-melt adhesive curable with ionizing radiation |
CA1274647A (en) * | 1986-06-25 | 1990-09-25 | Takahisa Iwahara | Curable isobutylene polymer |
DE3629237A1 (en) * | 1986-08-28 | 1988-03-03 | Henkel Kgaa | ALKOXYSILANE-TERMINATED, MOISTURIZING POLYURETHANES AND THEIR USE FOR ADHESIVE AND SEALANTS |
CA1281149C (en) * | 1986-09-30 | 1991-03-05 | Fumio Kawakubo | Curable composition |
JP2512468B2 (en) * | 1987-04-13 | 1996-07-03 | 鐘淵化学工業株式会社 | Curable resin composition |
JP2750135B2 (en) * | 1988-11-29 | 1998-05-13 | サンスター技研株式会社 | Primer for moisture cross-linked polyolefin |
JP3037579B2 (en) * | 1995-03-17 | 2000-04-24 | サンスター技研株式会社 | Moisture-curable polymer composition and method for producing the same |
US6060560A (en) * | 1997-05-23 | 2000-05-09 | Shell Oil Company | Polyurethane compositions made from hydroxy-terminated polydiene polymers |
US6121354A (en) * | 1998-11-19 | 2000-09-19 | Bostik, Inc. | High performance single-component sealant |
WO2003014248A2 (en) * | 2001-08-07 | 2003-02-20 | National Starch And Chemical Investment Holding Corporation | Adhesion promoting resins with cross-linking properties |
US6803412B2 (en) * | 2003-03-13 | 2004-10-12 | H.B. Fuller Licensing & Financing Inc. | Moisture curable hot melt sealants for glass constructions |
-
2005
- 2005-12-08 US US11/297,757 patent/US7405259B2/en active Active
-
2006
- 2006-04-12 AU AU2006242705A patent/AU2006242705B2/en not_active Ceased
- 2006-04-12 BR BRPI0608331-5A patent/BRPI0608331A2/en not_active Application Discontinuation
- 2006-04-12 EP EP06749953.3A patent/EP1874840B1/en active Active
- 2006-04-12 WO PCT/US2006/013752 patent/WO2006118766A1/en active Application Filing
- 2006-04-12 KR KR1020077027791A patent/KR101359995B1/en active IP Right Grant
- 2006-04-12 CA CA002605264A patent/CA2605264A1/en not_active Abandoned
- 2006-04-12 RU RU2007144208/04A patent/RU2007144208A/en unknown
- 2006-04-12 JP JP2008508900A patent/JP4988709B2/en active Active
- 2006-04-12 EP EP20153362.7A patent/EP3666808B1/en active Active
-
2007
- 2007-11-05 NO NO20075580A patent/NO20075580L/en not_active Application Discontinuation
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4118536A (en) * | 1976-10-08 | 1978-10-03 | Minnesota Mining And Manufacturing Company | Silane-terminated polycarbodiimide primers and composite coatings therefrom |
JPS6147774B2 (en) | 1978-06-28 | 1986-10-21 | Ube Industries | |
JPS6257480B2 (en) | 1978-10-07 | 1987-12-01 | Yunibaasaru Kongeitetsudo Botsukusu Mashiinari Hoorudeingu Ag | |
JPS5682863U (en) | 1979-11-30 | 1981-07-04 | ||
JPS6257478B2 (en) | 1980-05-08 | 1987-12-01 | Tokura Kk | |
JPS6257479B2 (en) | 1981-03-31 | 1987-12-01 | Fuji Oil Co Ltd | |
JPS57207663A (en) | 1981-06-15 | 1982-12-20 | Kongo Furotsukingu Kk | Hot-melt adhesive composition |
JPS59174672A (en) | 1983-03-23 | 1984-10-03 | Kao Corp | Hot-melt adhesive |
JPS59172575A (en) | 1983-03-23 | 1984-09-29 | Kao Corp | Hot-melt adhesive and its preparation |
JPS61218673A (en) | 1985-03-25 | 1986-09-29 | Agency Of Ind Science & Technol | Hot-melt adhesive curable with ionizing radiation |
JPS61218672A (en) | 1985-03-25 | 1986-09-29 | Agency Of Ind Science & Technol | Hot-melt adhesive curable with ionizing radiation |
JPS61218631A (en) | 1985-03-25 | 1986-09-29 | Agency Of Ind Science & Technol | Crosslinkable hot-melt adhesive |
JPS6289782A (en) | 1985-06-07 | 1987-04-24 | Asahi Glass Co Ltd | Hot-melt adhesive |
JPH03259981A (en) | 1990-03-12 | 1991-11-20 | Kuraray Co Ltd | Hot-melt adhesive composition |
JPH09165565A (en) | 1995-12-14 | 1997-06-24 | Kuraray Co Ltd | Adhesive composition |
US20020082333A1 (en) * | 2000-09-13 | 2002-06-27 | Rudiger Herpich | Silica gel-containing rubber compounds with organosilicon compounds as compounding agent |
US6641922B2 (en) * | 2001-01-17 | 2003-11-04 | A. Andrew Shores | Silicone and ionically modified isocyanate adduct |
Also Published As
Publication number | Publication date |
---|---|
US20060247370A1 (en) | 2006-11-02 |
BRPI0608331A2 (en) | 2009-12-29 |
AU2006242705B2 (en) | 2011-03-03 |
NO20075580L (en) | 2008-01-28 |
EP1874840B1 (en) | 2020-06-03 |
US7405259B2 (en) | 2008-07-29 |
KR20080013957A (en) | 2008-02-13 |
JP4988709B2 (en) | 2012-08-01 |
RU2007144208A (en) | 2009-06-10 |
EP1874840A1 (en) | 2008-01-09 |
EP3666808B1 (en) | 2021-06-23 |
WO2006118766A1 (en) | 2006-11-09 |
KR101359995B1 (en) | 2014-02-21 |
JP2008539305A (en) | 2008-11-13 |
CA2605264A1 (en) | 2006-11-09 |
AU2006242705A1 (en) | 2006-11-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1874840B1 (en) | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same | |
US20060247369A1 (en) | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same | |
EP1951781B1 (en) | Solvent resistant polyurethane adhesive compositions | |
EP2057203B1 (en) | Silylated polyurethane compositions and adhesives therefrom | |
US7781513B2 (en) | Two-part moisture-curable resin composition and adhesive, sealant and coating compositions based thereon | |
JP5653368B2 (en) | Moisture curable silylated polymer with improved storage stability | |
EP2231740B1 (en) | Moisture-curable silylated polyurea and adhesive, sealant and coating compositions containing same | |
US8247079B2 (en) | Laminate containing a silylated polyurethane adhesive composition | |
EP3494162B1 (en) | Non-tin catalyst for curing alkoxysilyl-containing polymer | |
US8178614B2 (en) | Laminate containing solvent resistant polyurethane adhesive compositions | |
JP4623875B2 (en) | Moisture curable adhesive polyurethane adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
AC | Divisional application: reference to earlier application |
Ref document number: 1874840 Country of ref document: EP Kind code of ref document: P |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: FRYE, ROBERT L. Inventor name: ECKBERG, RICHARD P. Inventor name: GRISWOLD, ROY M. |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20200923 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C09J 175/04 20060101ALI20210201BHEP Ipc: C08G 18/10 20060101AFI20210201BHEP Ipc: C08G 18/69 20060101ALI20210201BHEP |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20210311 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AC | Divisional application: reference to earlier application |
Ref document number: 1874840 Country of ref document: EP Kind code of ref document: P |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602006060101 Country of ref document: DE Ref country code: AT Ref legal event code: REF Ref document number: 1404253 Country of ref document: AT Kind code of ref document: T Effective date: 20210715 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210923 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1404253 Country of ref document: AT Kind code of ref document: T Effective date: 20210623 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210924 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20210623 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211025 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602006060101 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20220324 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20220430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220412 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220430 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220412 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230513 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20060412 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210623 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240423 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240429 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240430 Year of fee payment: 19 |